Coordination Chemistry Reviews 276 (2014) 112–152

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Coordination Chemistry Reviews

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Review

Ruthenium pincer complexes: Ligand design and complex synthesis

Hussein A. Younus a,b,d , Nazir Ahmad a,b , Wei Su a,b , Francis Verpoort a,b,c,e,∗
a
Laboratory of Organometallics, Catalysis and Ordered Materials, State Key Laboratory of Advanced Technology for Materials Synthesis and Processing,
Center for Chemical and Material Engineering, Wuhan University of Technology, Wuhan, China
b
Department of Applied Chemistry, Faculty of Sciences, Wuhan University of Technology, Wuhan 430070, China
c
Tomsk Polytechnic University, Lenin Avenue 30, 634050 Tomsk, Russian Federation
d
Chemistry Department, Faculty of Science, Fayoum University, Fayoum 63514, Egypt
e
Ghent University, Global Campus Songdo, 119 Songdomunhwa-Ro, Yeonsu-Gu, Incheon, South Korea

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
1.1. General considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
1.2. Nomenclature of pincer ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
2. Synthesis of pincer ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
2.1. Tuning of the pincer ligand . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
2.2. Pyridine-based pincer ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
2.2.1. Phosphine-containing pincer ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
2.2.2. NHC-containing pincer ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
2.2.3. NNN pincer ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
2.2.4. CNN pincer ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
2.3. Benzene-based pincer ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
2.3.1. Symmetrical pincer ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
2.4. Miscellaneous pincer ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
3. Synthesis of ruthenium pincer complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
3.1. Direct metallation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
3.2. C H bond activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
3.3. Si H bond activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
3.4. Transmetallation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
3.5. Trans-cyclometallation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
4. Effects of the pincer complex structure on the catalytic activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
4.1. Hemilability and non-innocent behavior of the pincer ligand . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
4.2. Flexibility of the pincer framework (aliphatic versus aromatic) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
5. Conclusion and future prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149

a r t i c l e i n f o a b s t r a c t

Article history: Active transition–metal complexes based on relatively inexpensive metals are considered to be a desirable
Received 6 March 2014 method for sustainable human industrial growth. Considering their cost efficiency, ruthenium complexes
Received in revised form 16 June 2014 are gaining increasing attraction, instead of palladium, rhodium, and iridium. Among the ruthenium
Accepted 18 June 2014
complexes, ruthenium pincer complexes (RPCs) have received much attention due to their outstanding
Available online 26 June 2014
performance. Various strategies have been developed for pincer ligand design and RPC synthesis, which
indicate that ligand design is a key feature of pincer chemistry. In addition, electronic and steric effects,
Keywords:
C H activation
Direct hydrogenation

∗ Corresponding author at: Ghent University Global Campus Songdo, 119 Songdomunhwa-Ro, Yeonsu-Gu, Incheon, South Korea.
E-mail addresses: Francis@whut.edu.cn, Francis.verpoort@ugent.be (F. Verpoort).

http://dx.doi.org/10.1016/j.ccr.2014.06.016
0010-8545/© 2014 Elsevier B.V. All rights reserved.
 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152
Direct metallation hemilability, non-innocent behavior, and the flexibility of the pincer ligand have significant effects on the
Pincer ligand catalytic performance of RPCs in hydrogenation and dehydrogenation reactions.
Ruthenium pincer complex
Transfer hydrogenation
Trans-cyclometallation
Trans-metallation
1. Introduction
1.1. General considerations
In the field of homogeneous catalysis, the choice of an appropri-
ate ligand is very important and critical for fine-tuning the catalytic
activities and stereoselectivities of metal complexes. Steric and
electronic properties can greatly influence the nature of the reac-
tive species and determine the course of reactions. Pincer-based
metal catalysts are exceptional in determining the balance of sta-
bility versus reactivity. This balance can be controlled by systematic
ligand modifications and/or variation of the metal center, thereby
allowing enhancement of the metal complex reactivity, stability,
and reaction selectivity. Therefore, developing a tridentate pincer
ligand is one of the most fruitful strategies for obtaining well-
defined metal–ligand bonds.
“Pincer ligands” [1] are tridentate ligands that bind tightly
to three adjacent coplanar sites of a metal center, mostly in a
meridional fashion [2], thereby resulting in the formation of two
stable cyclometallated rings. The two cyclometallated rings may be
five-membered [3], six-membered [4], or hybrids of five- and six-
membered rings [5]. Since the pioneering work reported by Shaw
[6] and Van Koten and Noltes [7] in the 1970s using the so-called
PCP and NCN type metal complexes with pincer ligands, pincer-
type complexes have occupied very important roles in chemistry
and chemistry-related disciplines. A wide variety of pincer struc-
tures have been designed with various transition metals as well
as different ancillary ligands. Therefore, the range of pincer metal
complexes is extremely broad and increasing continuously (Fig. 1)
[3,8–23].
Ruthenium complexes exhibit diverse beneficial characteristics
including high electron transfer ability [24], high coordination abil-
ity to hetero-atoms, low redox potentials [25], Lewis acid activity
[26], and unique reactivity with metal species and intermediates,
such as oxo-metals, metallacycles, carbenes, and Schiff base com-
plexes [27–32]. Consequently, ruthenium catalysis is one of the
most important catalytic tools in organic synthesis [33]. In the
last year, ruthenium pincer complexes (RPCs) represented around
13% of the total research conducted in the pincer complex area
(Fig. 2). Large numbers of novel and useful reactions have been
developed using stoichiometric and catalytic amounts of ruthe-
nium complexes. Compared with traditional ruthenium catalysts,
pincer complexes often offer higher efficiency and selectivity, as
Fig. 1. Publications related to pincer complexes since 2004.
Source: Sci Finder.
113
© 2014 Elsevier B.V. All rights reserved.
well as functional group tolerance. Excellent reviews have dis-
cussed the synthesis and catalytic applications of palladium [14]
and iridium [16] pincers, but only a few catalytic applications of
ruthenium pincers [8,12,17,34] have been reviewed, and no pre-
vious reviews have addressed the design and synthesis of RPCs.
Therefore, this review presents the different methods developed
for the design and synthesis of RPCs over the last decade.
1.2. Nomenclature of pincer ligands
The nomenclature of the pincer ligand indicates the attachment
points between the transition metal and the three atoms that coor-
dinate with the metal center, the hetero/C-atoms of the side arms,
and the central atom. If there are two spacers between the central
moiety (pyridine, benzene, etc.) and the donor atoms of the side
arms are C-atoms, or if there are no spacers, it will not be included
in the symbol of the pincer ligand. However, if there are spacers
and one or both of them are non-carbon atoms, the pincer ligand
name indicates the position and type of the spacer as a superscript
to the original attachment points. For example, pincer ligands of
the type PNP with N/NH spacers between N and P are denoted as
PN NN P, and as PO NO P in the same manner. If the pincer ligand has
a CH spacer on one side and an N/NH spacer on the other side, it
will be symbolized as PN NC P. In addition, the alkyl or the aryl group
attached to the donor atom is included in the name as superscript
for the donor atom, e.g., PNPiPr and PNPPh . When a N-heterocyclic
carbene is one of the donor groups, the symbol of the pincer ligand
indicates that the donor carbon atom is part of the N-heterocyclic
carbene, e.g., (NHC)CNN shows that the first C-atom is part of the
carbene. In this review, this is indicated as a superscript for the C-
atom so the symbol is CNHC NN to confirm with the rules for the
nomenclature of whole pincer ligands.
Fig. 2. Percentage of publications in 2013 related to pincer complexes with different
metal ions.
Source: Sci Finder.
114 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152
Z = C, N, S, Si, P, B, etc.
X = CH2, NH2(R), O, CO, CS, etc.
E = NR2, PR2, P(OR)2, OR, OPR2, OP(OR)2, SR, SeR, AsR, SiR, etc.
R = H, electron donating and electron withdrawing groups
Fig. 3. General pincer ligand structure.
2. Synthesis of pincer ligands
2.1. Tuning of the pincer ligand
Ligand design is an increasingly important component of syn-
thetic chemistry because of the subtle control that ligands exert
on the metal center with which they are coordinated. Pincer lig-
ands are tridentate ligands, which usually feature a central aromatic
ring that is ortho,ortho-disubstituted with two electron-donor sub-
stituents (E). During the last 40 years, the pincer-ligand platform
has established multifunctional building blocks, which have been
used successfully in a number of various applications, e.g., bond
activation [8], organic synthesis [35], homogeneous and heteroge-
neous catalysis [36], polymer chemistry [37,38], photochemistry
[39–41], sensors [42,43], switches [44], and as biomarkers in medic-
inal chemistry [45]. The wide variety of applications of pincer type
complexes is a direct indication of one of the ligands’ most attrac-
tive features, i.e., the number of options for tuning their electronic
and steric properties without affecting the ligand’s ability to bind
the metal center.
The most common method used to synthesize RPCs involves
the introduction of the ruthenium source to a predesigned pincer
ligand. The synthesis is usually based on a straightforward reaction
but it sometimes includes functional group conversion. However,
sophisticated ligand design is usually involved in pincer chemistry.
For example, unsymmetrical pincer complexes with two different
donor atoms (EZE ) have been shown to possess higher catalytic
properties compared with their symmetrical analogs [46–48]. This
high catalytic activity could be attributed to the hemilability of the
unsymmetrical pincer ligand with respect to the metal center of the
complex. Even a slight change in the pincer ligand structure, such as
replacing one of the donor atoms in the side arms of the ligand, has
a significant effect on the catalytic activity as well as the reaction
product [49,50]. In addition, asymmetric catalysis can be achieved
using chiral pincer ligands [51–54]. Moreover, the steric effect of
the substituent on the chiral moiety clearly affects the enantiose-
lectivity of the product [55]. Therefore, careful pincer ligand design
depends on the target catalytic reaction, the substrates used, and
the catalytic process conditions.
Modification of the pincer ligand backbone can be achieved
in a variety of ways. The most common method is changing the
ring size (five-, six-, or seven-membered ring), changing the ring
nature (aromatic versus nonaromatic), or eliminating the ring itself
to build an acyclic pincer ligand. The nature of the side arms also
affects the design of the pincer ligand by conferring specific elec-
tronic and steric properties. The donor group (E) (Fig. 3) can be
a heteroatom, part of a heterocyclic group, or an NHC. Moreover,
identical donor groups can be used to build a symmetrical pin-
cer (EZE) or different groups to construct an unsymmetrical pincer
(EZE ). The most common differences are: (i) soft vs. hard donors,
(ii) the rigidity of their binding to the metal center, (iii) the steric
constraints on their substituents, and (iv) the ligand type (e.g.,
neutral, charged, Lewis acidic, or Lewis basic). The donor groups
(E) are connected to the central backbone by spacers (X), such as
methylene groups ( CH2 ), amines ( NR ), or oxygen atoms
( O ). The spacer variation can generate chiral pincers, thereby
modifying the spacers to control the enantioselectivity of the cat-
alyst. Furthermore, changing the length of the spacer has a direct
effect on the coordination pocket of the pincer ligand and on its
spatial behavior during coordination. A further electronic influence
may be exerted by alkyl or aryl groups attached to the aromatic sys-
tem, thus remote electronic modifications can be achieved by vary-
ing the R group anchored to the backbone of the ligand. In addition,
the nature of the central donor has a direct impact on the overall
properties of the metal center. Replacements of the central carban-
ion with isoelectronic nitrogen [56,57], silicon [58–61], phosphorus
[62,63], or boron anion [64–66] have also been achieved in suc-
cessful syntheses and explored further in recent years. Thus, both
neutral and anionic pincers can be obtained (Fig. 3).
Various pincer structures have been reported for ruthenium
metal ions and different synthetic strategies are available. The final
decision when selecting a convenient procedure for synthesizing
the pincer will depend on the mean skeleton required, the spacers
between the central donor atom (Z) and the donor groups (E), and
mainly on the arms of the pincers (X).
2.2. Pyridine-based pincer ligands
Pyridine-based pincer transition metal complexes are of par-
ticular importance due to their reactivity and flexibility for
modification, thus most of the reported RPCs are based on the
pyridine skeleton. Consequently, we discuss the different synthetic
methods reported for the various types of pincers, such as PNP, PNN,
PNS, CNN, CNHC NN, CNH CNCNHC , and NNN, with different structures
that serve as ligands for ruthenium complexes. Different synthetic
strategies have been used for the direct synthesis of tridentate lig-
ands with a central pyridyl fragment.
2.2.1. Phosphine-containing pincer ligands
2.2.1.1. Symmetrical ligands (PNP, PN NN P, PO NO NP). Symmetrical
PNP pincer ligands are easier to produce compared with non-
symmetrical ones. In general, the reaction starts with a symmetrical
ligand by applying an instant modification of the two ligand
sides. Fitting the two side arms of the pincer with a halide
atom followed by nucleophilic substitution using a phosphine
source is the desirable method for building the PNP pincers.
Pyridine-based PNP pincer ligands with a methylene group as
a spacer have been synthesized via direct nucleophilic sub-
stitution of 2,6-bis(chloro/bromo-methyl)pyridine using sodium
diphenylphosphide [67]. The addition of a secondary phosphine
to 2,6-bis(chloromethyl)pyridine followed by selective deproto-
nation using triethylamine was also described by Milstein et al.,
where this method is more general and it avoids potential issues
with unstable phosphide intermediates [68]. Rieger et al. described
the synthesis of a series of PNP pincers with different aromatic
substituents at phosphane via the treatment of diarylphosphanes
with 2,6-bis(chloromethyl)-pyridine in the presence of a base,
such as potassium t-butoxide [69]. Kawatsura and Hartwig synthe-
sized the PNP pincer ligand via selective lithiation of 2,6-lutidine
followed by reaction of the lithiated species with chlorophos-
phine reagents [70]. The yield of the latter reaction is slightly
lower than the two-step addition using secondary phosphines,
but the reagents are more readily available and less expensive.
Scriban and Glueck reported the platinum-catalyzed asymmet-
ric phosphination of 2,6-bis(bromomethyl)pyridine with PHMeIs
(Is = 2,4,6-tris(isopropyl)phenyl) to generate the corresponding P-
stereogenic diphosphine 3MeIs with up to 72% ee [71]. Recently,
Toste et al. developed a ruthenium catalyst for the enantiose-
lective alkylation of chiral racemic secondary phosphines with
2,6-bis(chloromethyl)pyridine (Scheme 1).
 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152
Scheme 1. Synthesis of PNP pincer ligands.
For the PNP family of pincer ligands, the steric, electronic, and
stereochemical parameters can be manipulated via modifications
of the benzylic positions and/or the phosphino alkyl/aryl groups to
control the reactivity at the metal center. However, stereochemical
parameters are comparatively difficult to modify and they often
require multistep syntheses and expensive starting materials. In
addition, pincer behavior investigations have indicated that the
methylene groups on the PNP ligand play significant roles in the
reactivity of metal complexes. These CH2 groups are susceptible to
deprotonation by an external base or the transition metal itself,
thereby resulting in dearomatization of the ligand [17]. Conse-
quently, replacing the reactive -CH2 - spacer on PNP with an O-
or N- linking unit in the PO NO P and PN NN P pincer type ligands,
respectively, may avoid the possibility of ligand deprotonation. The
neutral PO NO P pincer ligand 7 was prepared in a direct manner by
the treatment of 2,6-dihydroxypyridine hydrochloride with dialkyl
chlorophosphine in the presence of a base (Scheme 2). Changing the
base has a significant effect on the reaction yield and reaction time,
hence an excess of triethylamine at 65 ◦ C in tetrahydrofuran (THF)
yielded the product at 57% after one week [72], whereas a mixture
of NNNN-Tetramethylethylenediamine (TEMDA) and NEt3 in the
same conditions yielded the product at 75% within 20 h [73]. This
ligand can be synthesized at a higher yield (85%) and purity (99%)
by combining aspects of the two methods, i.e., using a mixture of
TEMDA and NEt3 in THF at 75 ◦ C for one week [74].
Kirchner reported the synthesis of a series of modularly
designed PNP ligands based on pyridine-bearing NH-groups as
spacers, which are easily accessible for the modification of steric,
electronic, and stereochemical properties [75–78]. This method
was first reported by Haupt et al. [79,80] and then developed
by Kirchner for the synthesis of a large collection of PNP and
PCP pincers. The ligands were prepared by the treatment of 2,6-
diaminopyridine with 2 equiv. of the respective R2 PCl compound
in the presence of a base, e.g., NEt3 and/or n-BuLi. This method
failed in the case of N,N-dialkylated diaminopyridines [17], where
Scheme 2. Straightforward synthesis of PO NO P pincer ligands.
115
several phosphorus-containing species were formed instead,
including tetraphenyldiphosphine and tetraphenyldiphosphine
monoxide. However, the synthesis of these ligands could be
achieved via a two-step procedure: the addition of 1 equiv. of
Ph2 PCl to N,N-dialkyl-2,6-diaminopyridine in the presence of n-
BuLi, followed by the addition of another equivalent of Ph2 PCl and
n-BuLi to yield the desired PNP ligands 9 (Scheme 3). The former
two examples of PNP pincer ligands with O/N spacers result in a
readily accessible and tunable pincer ligand.
2.2.1.2. Unsymmetrical ligands (PNN, PNS). Modification of the pin-
cer “arm” has a profound effect on the catalytic activity of the pincer
complex. The replacement of one phosphine group by a weaker
donor may facilitate ligand dissociation from the metal center and
it may increase the hemilability of this type of pincer complex,
thereby increasing its catalytic activities accordingly [81]. Thus,
mixed or hybrid pincer systems based on pyridine have also been
designed and developed for ruthenium complexes, which increase
the probability of potential “hemilability” in the newly designed
ligand. Designing and constructing unsymmetrical pincer ligands
is a multistep process and this is sometimes not an easy task. Start-
ing with a symmetrical ligand source and modification with two
different donor sites in two separate steps is one possible synthetic
route. An easier method utilizes an unsymmetrical ligand source to
build the donor sites. PNN pincer ligand 12 was synthesized from
the commercially available 2,6-lutidine by refluxing with 1 equiv.
NBS, thereby resulting in the formation of 2-bromomethyl-
6-methylpyridine 10, which can easily undergo nucleophilic
substitution with diethylamine to obtain 6-diethylaminomethyl-
6-meth-ylpyridine 11 with a yield of 66%. This intermediate
was deprotonated with n-BuLi at 0 ◦ C and then reacted with
di-t-butylchlorophosphine at −78 ◦ C to form the ligand (2-(di-tert-
butyl-phosphinomethyl)-6-diethylaminomethyl)pyridine (PNN)
12 with a yield of 70% [82,83] (Scheme 4).
Furthermore, exploration of the replacement of the amine arm
in the PNN pincer ligand with a thioether group was studied
by Milstein group [84]. The PNS pincer ligand was synthesized
using a procedure similar to that reported by Szabo for the prepa-
ration of a PCS ligand [85]. Thus, reacting LiPtBu2 (BH3 ) with
2,6-bis(chloromethyl)pyridine yielded a mixture of monophos-
phine, diphosphine, and unreacted 2,6-bis(chloromethyl)pyridine.
After isolating the monophosphine 13, treatment with an excess
of sodium 2-methyl-2-propanethiolate obtained the borane-
protected PNS ligand 14 with a yield of 99%. Deprotection of the PNS
116 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152

Scheme 3. Synthesis of PN NN P pincer ligands.

Scheme 4. Synthesis of the hybrid PNN pincer ligands.

Scheme 5. Synthesis of the hybrid PNS pincer ligand.

ligand by refluxing in diethylamine generates the PNS pincer ligand
15 as an air-sensitive white solid with a yield of 66% (Scheme 5).
Unfortunately, it is clear that the process used to prepare the air
sensitive PNS pincer ligand generated a mixture of products in more
than one step.
The 2,2-bipyridine ligand has been used extensively as a
metal-chelating ligand due to its robust stability and ease of func-
tionalization, thus bipyridine is the most widely used ligand [86].
Milstein et al. reported highly active bipyridine-based RPCs. The
electron-rich tridentate PNN ligand based on 2,2-bipyridine, BPy-
PNN, has been synthesized in many ways. In most cases, the
synthesis starts from 6-methyl-2,2 -bipyridine (BPy-Me) 18, which
has been prepared via a Stille-type cross-coupling reaction by
refluxing 2-bromo-6-picoline 17 with 2-tributylstannyl-picolines
in toluene, and in the presence of Pd(PPh3 )4 as a catalyst [87,88].
Treatment of 18 with 1 equiv. of LDA followed by trapping with
TMSCl produced 6-(trimethylsilyl)methyl-2,2 -bipyridine 19. The
former reacts with hexachloroethane to yield 6-chloromethyl-2,2 -
bipyridine (BPyCH2 Cl) [89]. Treatment of BPyCH2 Cl with 1.2 equiv.
of di-tert-butyl phosphine in MeOH in a sealed tube at 50 ◦ C for
48 h followed by abstraction of the liberated HCl with triethylamine
at room temperature generated the Bpy-t-Bu PNN ligand 21 [68]
(Scheme 6). In addition, synthesis of the PNN pincer ligand based
on bipyridine has been extended to obtain more flexible PNN-type
pincer ruthenium complexes [90]. Methyl bipyridinemethane was
prepared by reacting 2,6-lutidine with 2-fluoropyridine and n-BuLi
in THF, where alkylation of the bridging methylene group was per-
formed by deprotonation using n-BuLi with the addition of slight
excess of iodomethane in THF or 1,4-diiodobutane, and finally the
phosphination of 24a,b was achieved using a slight excess of n-
BuLi and ClPt Bu2 to produce the PNN pincer ligand 25a,b. Ligand
28, which bears a bridging oxygen atom, was prepared using the
method reported by Buchwald [91] (Scheme 7).
Recently [92], Gusev et al. reported the straightforward synthe-
sis of a PNN pyridine-based pincer ligand via the condensation of
2-picolyl aldehyde and 2-(alkyl/aryl phosphino)ethylamine in THF
at ambient conditions, followed by reduction of the imine group
using NaBH4 (Scheme 8). Chen et al. designed a non-symmetrical
pyridine-based pincer ligand bearing a phosphine using NH as a
spacer on one side and an oxazoline ring as a relatively weaker
 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152 117

Scheme 6. Synthesis of the PNN pincer ligand based on bipyridine.

Scheme 7. Synthesis of the flexible PNN pincer ligand with different spacers.

Scheme 8. Straightforward synthesis of PNN pincer ligands.

Scheme 9. Synthesis of PN NC N pincer ligands bearing a hemilabile oxazoline ring.

118 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152
Scheme 10. Synthesis of the symmetrical CNHC NCNHC pincer ligand.
donor on the other side, with the aim of increasing the hemilability
of the complex. The PN NC N pincer was prepared from commercially
available 6-bromopicolinic acid, as shown in Scheme 9 [93–95].
2.2.2. NHC-containing pincer ligands
NHC ligands are often considered to be phosphine mimics, but
they are generally more electron-rich than phosphines and are
more tightly bound to the metal. As a consequence, organometallic
complexes with N-heterocyclic ligands usually exhibit higher reac-
tivity, better stability, and a broader variety of catalytic activities
compared with those involving phosphine ligands. Therefore, N-
heterocyclic ligands have become more attractive in homogeneous
catalysis and organic synthesis [96–99]. Incorporation of the NHC
moiety into the pincer backbone has allowed the synthesis of sev-
eral types of NHC-containing pincer-type ligands that are neutral
[100,101] and monoanionic [102], where the NHC moiety functions
as a lateral donor or as the backbone [10]. RPCs can incorporate NHC
ligands in one/two sides of the pincer and pincers have even been
described with two different NHC ligands that coordinate to the
same Ru center.
2.2.2.1. CNHC NCNHC pincer ligands. CNC ligands have a wide range
of applications where the early transition metals support com-
plexes with significant stability in a range of oxidation states,
thereby providing convenient platforms for further derivatization.
The symmetrical CNHC NCNHC pincer ligands are easily acces-
sible by the direct combination of the NHC source with the
bis-halogenated pyridine ring. Thus, heating 2,6-dibromopyridine
with 2 equiv. of 1-alkyl imidazole in a sealed tube for one
week at 140 ◦ C produced the pincer ligand. Treatment of
Scheme 11. Synthesis of CNHC NCNHC and CNHC NN pincer ligands.
2,6-[(o-dialkyl)phenylimidazolium]pyridine dibromide 40a,b with
2 equiv. of KHMDS produced the free carbene 41a,b with a yield
of 70–80%, which is an off-white crystalline product that can
be handled as a solid under nitrogen at room temperature for
hours without exhibiting decomposition, and the structure of
41a was confirmed by X-ray crystallography analysis [103]. The
molecule is strictly planar and it adopts a conformation where
the carbene and pyridine lone pairs are mutually anti, probably
to minimize lone pair repulsions. More conveniently, the sym-
metrical CNHC NCNHC pincer ligand 45 with two methylene spacers
was obtained by combining 2 equiv. of substituted imidazoles with
the bis bromomethyl pyridine under reflux conditions in acetone
[104,105] (Scheme 11A). The bis triazole carbene-based CNHC NCNHC
pincer ligand is more readily accessible via ruthenium-catalyzed
azide-alkyne cycloaddition (RuAAC) (Click reaction) [106]. Thus,
“clicking” diethynylpyridine and alkyl azide in dioxane produced
bis(1,2,3-triazolylidene)pyridine ligand, where methylation using
trimethyloxonium tetrafluoroborate yielded the corresponding
symmetrical CNHC NCNHC pincer ligands 44 [107] (Scheme 10).
2.2.2.2. CNHC NN pincer ligands. In general, two approaches are used
to construct a CNHC NN pincer based on pyridine as a central moi-
ety. The first approach introduces the imidazole moiety (source of
NHC) followed by alkylation (or N-substituted imidazole at once),
and then combining the ligand produced with the N-donor. In
most cases, nucleophilic substitutions are used to introduce the N-
donor into the ligand structure, but the N-donor could be built in
the pincer ligand. The second approach starts with the NN donor,
which is combined with the NHC source. Sanchez et al. reported
the synthesis of unsymmetrical neutral N-heterocyclic carbene
 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152
Scheme 12. Synthesis of the CNHC NN pincer ligand based on bipyridine.
pincer-type ligands CNHC NN for Ru(II) complexes [108]. The pin-
cer ligand with NHC as a hard donor and pyrrolidine as a soft
donor was designed in the hope that the hemilability of the pyrro-
lidine moiety might act as an internal base, possibly eliminating
the need to add a base during catalysis. Starting from the sym-
metrical source, the unsymmetrical pincer was obtained first by
introducing the N-substituted imidazole moiety, followed by ami-
nation of the alkyl halide arm. The CNHC NN ligand was prepared
by treatment of 2,6-bis(bromomethyl)pyridine with a substoi-
chiometric amount of 1-aryl-1H-imidazole in refluxing acetone
to obtain the corresponding imidazolium salt 46. The monoalky-
lated salt undergoes a nucleophilic substitution with the secondary
amine in the presence of a base to produce the CNN pincer ligand
47 [104,105] (Scheme 11B). CNHC NN based on bipyridine has been
prepared in straightforward manner (Scheme 12) by refluxing
6-(chloromethyl)-2,2 -bipyridine 20 with 1-mesityl-1H-imidazole
38a in dry acetonitrile with a yield of 86% [109].
Another approach has also been developed for the synthe-
sis of the CNHC NN pincer ligand with a pyrazole moiety as an
N-donor. A pyridyl-based (pyrazol-3-yl)-N-heterocyclic carbene
pincer ligand was synthesized via two different pathways. The first
procedure exploits a ligand source with two different functional
groups in a two-step modification process. Methyl 6-bromo-
2-pyridinecarboxylate 49 reacts with imidazolatopotassium in
diglyme for 60 h, followed by Claisen condensation of the prod-
uct with 3,3-dimethyl-2-butone, and subsequent reaction with
hydrazine hydrate generates 2-(imidazol-1-yl)-6-(5-tert-butyl-
1H-pyrazol-3-yl)pyridine 51. When alkylated using 1-iodoalkane
in refluxing acetonitrile, the former yields the CNHC NN pincer ligand
Scheme 13. Synthesis of CNHC NN without a spacer, which comprises pyrazole and imidazolium moieties.
119
52 [110] (Scheme 13). The second method utilizes the commer-
cially available 2,6-dibromopyridine as a starting compound, which
has the capacity to synthesize multi-substituted pyrazole moi-
eties. The first step involves the coupling of 2,6-dibromopyridine
and pyrazole using the catalytic system Pd(OAc)2 /PPh3 [111].
Next, the heteroarylation of imidazole with 2-bromo-6-(pyrazol-
1-yl)pyridine followed by N-alkylation of the product with
1-iodoalkane generates the desired product 56 [112] (Scheme 13).
2.2.3. NNN pincer ligands
The potential of tridentate NNN ligands such as Pybox
[113], 2,6-bis(imino)pyridines [114], terpyridines [115], and other
symmetrical NNN ligands has been demonstrated in different appli-
cations. The synthesis of this type of symmetrical pincer ligand
has been discussed previously and it is not repeated here. Sev-
eral 2,6-bis(pyrazol-1-yl)pyridine (BPP) derivatives of 58 have
been synthesized as NNN pincer ligands by Jameson et al. [116],
but the synthesis of the first neutral transition–metal complex
of these ligands was described only recently [117]. Symmetri-
cal NNN pincer ligands of the bis(pyrazolyl)pyridine type can
be prepared in a straightforward manner via the nucleophilic
substitution of 2,6-dichloropyridine, 2,6-dibromopyridine, or 2,6-
bis(bromomethyl)pyridine with a pyrazole salt [118] (Fig. 4).
Recently, Yu et al. reported the synthesis of a series of RPCs based
on unsymmetrical NNN pincer ligands. The unsymmetrical pyridyl-
based bis-pyrazole pincer ligand 61 was prepared by lithiation of
2-bromo-6-(3,5-dimethylpyrazol-1-yl)pyridine 54b with n-BuLi at
−78 ◦ C, followed by treatment with N,N-dimethylacetamide to pro-
duce the acetyl derivative 59a [119]. Claisen-Schmidt condensation
of the acetyl derivative with N,N-dimethylformamide dimethy-
lacetal (DMFDMA) yielded the ␤-amino-substituted enone [120],
which after condensation with hydrazine hydrate produced the
unsymmetrical NNN pincer ligand 61 [121] (Scheme 14).
The pyridyl-based pyrazolyl-imidazoly/benzoimidazolyl pincer
ligand 62 was also prepared by formylation of 2-bromo-6-
(3,5-dimethylpyrazol-1-yl)pyridine using DMF/n-BuLi followed by
condensation with o-phenylenediamine [48,122]. Moreover, the
imidazolyl moiety can be converted easily into its N-methyl analog.
It is worth mentioning that condensation of the carbonyl derivative
120 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152
Scheme 14. Synthesis of unsymmetrical NNN pincer ligands.
Fig. 4. Synthesis of symmetrical NNN pincer ligands.
59 with primary amines (e.g. 4-toluidine) in the presence of p-TsOH
in refluxing toluene yields the Schiff base, which after reduction
with NaBH4 in methanol produces the NNN pincer ligand, i.e.,
2-(aminomethyl)-6-(3,5-dimethylpyrazol-1-yl)pyridine 64 [123]
(Scheme 14).
A chiral pyridyl-based pyrazolyl oxazolinyl pincer ligand
with a pyrazolyl NH functionality was designed and prepared
in a sequence of reactions, which also started with 2-bromo-
6-(3,5-dimethylpyrazol-1-yl), as shown in Scheme 15 [124].
Copper-catalyzed cyanation of the 2-bromopyridine derivative
yielded compound 65, which reacted with alcohol to generate the
imidate intermediate. Cyclization of the imidate with chiral amino
alcohol yielded the chiral NNN pincer ligand 66. Another chiral NNN
pincer ligand of the pyridyl-based pyrazolyl oxazolinyl pincer type
was synthesized in a similar manner by condensation of 2-acetyl-
6-bromopyridine with DMFDMA, followed by cyclization with
hydrazine hydrate to produce 2-(pyrazol-1-yl)-6-bromopyridine.
Further treatment of ligand 68 in a similar manner obtained
ligand 69 [124]. Chiral pyridyl-based benzimidazolyl–oxazolyl
NNN ligand 73 was synthesized using the same procedure, which
started by the esterification of compound 70, followed by reaction
with the chiral amino alcohol. Cyclization was the next step, which
can be performed in two ways: treatment with thionyl chloride in
dichloroethane at 70 ◦ C for 4 h followed by reflux with an ethanolic
solution of sodium hydroxide overnight, or in a straightforward
reaction by heating its ethereal solution with boron trifluoride at
Fig. 5. CNN pincer ligand based on pyridine.
120 ◦ C [55]. In addition, the chiral mono-N-alkyl derivative and
the di-N-alkyl derivative of bis(benzimidazol-2-yl)-pyridine were
prepared by reacting bis(benzimidazol-2-yl)pyridine with 1 and
2 equiv. of 1-bromopropane in the presence of NaH [55].
The benzotriazolyl moiety has been utilized to construct
pyridyl-based benzimidazolyl–benzotriazolyl NNN pincer ligands.
Ligand synthesis begins by reacting 2,6-dibromopyridine with a
substoichiometric amount of benzotriazole in solvent-free con-
ditions to produce compound 74. Formylation of 74 followed
by condensation with 1,2-phenylenediamine generates the NNN
ligand, which can undergo N-methylation using MeI/NaH to yield
the ligand 77, which bears a benzotriazole and a benzimidazolyl
group [125] (Scheme 16).
2.2.4. CNN pincer ligands
Although NCN and PNP pincer ligands have been studied widely,
the CNN motif has received much less attention. The first exam-
ple of a CNN Ru pincer complex was reported very recently. The
type A CNN tridentate pincer ligand was designed to contain the 2-
aminomethylpyridine moiety (Fig. 5), which has a particularly high
ligand acceleration effect on the transfer hydrogenation of ketones
by ruthenium(II) [126].
The synthesis of a CNN pyridine based pincer ligand fre-
quently begins with 2-phenyl pyridine. The subsequent creation
of the N-donor at the 6-position or the modification of already
present functional groups can produce the final pincer ligand. The
same structure could also be assembled using the 6-substituted
NN ligand by incorporating a phenyl group. The type A CNN
pincer ligand can be prepared via different strategies using a
variety of starting compounds. The most recent method starts
with ␣-cyanation of 2-arylpyridine-N-oxide with trimethylsilyl
cyanide and dimethylcarbamyl chloride [127,128], followed by
reduction of the cyanide group to produce 2-aminomethyl-
6-aryl pyridine 81 [129]. The CNN pincer ligand with the
N,N-dimethylaminomethyl donor 82 can be prepared from 81 via
 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152 121

Scheme 15. Synthesis of unsymmetrical chiral NNN pincer ligands.

Scheme 16. Synthesis of pyridyl-based benzimidazolyl–benzotriazolyl NNN pincer ligands.

Scheme 17. Synthesis of achiral CNN pincer ligand based on pyridine.

122 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152
Scheme 18. Synthesis of chiral CNN pincer ligand based on pyridine.
Scheme 19. Synthesis of type B CNN pincer ligand.
formic acid-formaldehyde methylation [130] (Scheme 17). This
procedure is easier for synthesizing the type A CNN pincer and
more straightforward compared with the other reported routes for
synthesizing the same structure utilizing 6-bromopicolylaldehyde
Scheme 20. Synthesis of chiral pincer CNN ligands using a chemo-enzymatic approach.
Scheme 21. Synthesis of chiral (A) and racemic chiral (B) CNN pincer ligands based on benzo[h]quinoline.
[131] or 2,6-dibromopyridine [132] as starting materials. Chi-
ral pincers with the type A CNN structure have been prepared
by treatment of the corresponding ketones with hydroxylamine
hydrochloride and reduction of the oxime intermediate with
Zn/ammonium acetate/NH4 OH. Likewise, the optically active
ligand was obtained at a high yield via trifluoroacetic acid-mediated
hydrolysis of the (SS ,R)-N-(p-toluenesulfinyl)-2,2-dimethyl-1-(6-
phenylpyridin-2-yl)propylamine [129,133,134] (Scheme 18).
In a direct method, a CNN pincer ligand with structure B
that contained a pyrazole moiety as the N-donor was prepared
readily by palladium-catalyzed Suzuki coupling of 6-bromo-2-
(sub-pyrazol-1-yl)pyridine with p-tolylboronic acid with a yield of
86% [135] (Scheme 19).
Baratta described the synthesis of new chiral CNN pincer lig-
ands using a chemo-enzymatic approach [136]. Candida antarctica
lipase B was used for the resolution of racemic 6-bromo-1-(2-
pyridyl)-ethanol, which was obtained by the sodium borohydride
reduction of 67. After hydrolysis of the acetyl derivative, the
homochiral alcohol was converted into the corresponding azide
with diphenylphosphoroazidate (DPPA) in the presence of DBU.
To avoid epimerization, the reaction was performed at 0 ◦ C, which
resulted in a clean SN2 process that converted the alcohol (R)-90,
into the inverted azide (S)-91. Transformation of the azide into the
corresponding amine (S)-92 was achieved by treatment with Ph3 P
in refluxing THF/H2 O. Finally, Suzuki coupling with the appropriate
substituted phenyl and naphthyl boronic acids produced the HCNN
ligands (S)-93 (Scheme 20).
 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152
Scheme 22. General strategy for the synthesis of chiral non-racemic pincer ligands.
The synthesis of chiral and achiral CNN pincer ligands based
on benzo[h]quinoline has also been reported [137]. The reac-
tion of benzo[h]quinoline N-oxide with trimethylsilylcyanide
and dimethylcarbamyl chloride according to Fife’s procedure
for the regioselective cyanation of pyridine 1-oxides produced
benzo[h]quinoline-2-carbonitrile 95. Catalytic hydrogenation at
room temperature using a solution of benzo[h]quinoline-2-
carbonitrile in acetic acid generated the 2-aminomethylbenzo[h]-
quinoline compound 96 with a yield of 90% (Scheme 20A).
The substituted ligands 96b,c bearing a methyl and a tert-
butyl group, respectively, were synthesized by treatment of
Scheme 23. (A) General approach for symmetrical PCP pincer ligand synthesis on the left and an alternative method for non-nucleophilic phosphorus centers on the right.
(B) General protocol for the synthesis of symmetrical NCN pincer ligands.
Scheme 24. Synthesis of NCN and CNHC CCNHC pincer ligand via the “Click” reaction.
123
2-chlorobenzo[h]quinoline with bromotrimethylsilane to obtain 2-
bromobenzo[h]quinoline according to the Schlosser method [138].
The addition of n-butyl lithium at −78 ◦ C and DMA (R = Me), or
pivalonitrile (R = tBu), followed by reaction with NH2 OH·HCl in
ethanol resulted in the conversion of the ketones into the corre-
sponding oxime, where reduction generated the CNN pincer ligand
96b,c (Schemes 20B and 21).
Baratta et al. [139] described the application of stereo-
complementary biotransformations to the synthesis of both enan-
tiomers of 1-(6-phenylpyridin-2-yl)ethanamine 103 (Scheme 22).
The (S)-103 enantiomer was obtained via the lipase-mediated
kinetic resolution of the secondary alcohol (±)-101, followed by
Mitsunobu azidation, while baker’s yeast Saccharomyces cerevisiae
reduced the ketone derivative to give access to the enantiomeric
ligand (R)-103. This approach was then extended to the synthesis
of novel chiral 1-(benzo[h]quinolin-2-yl)ethanamine CNN pincer
ligands (R,S)-104.
2.3. Benzene-based pincer ligands
Pyridine-based pincers have been used as ligands for ruthenium
complexes, including many modifications in the mean skeleton,
donor atoms, and the spacers to generate the required properties,
but much less research has been performed using benzene-based
pincer ligands for ruthenium complexes. This may be related to
the unusual metal–ligand interactions of the pyridine-based pin-
cer ligands. This new mode of metal–ligand cooperation based on
the aromatization–dearomatization of pyridine-based pincer-type
ligands has been demonstrated in the activation of many unre-
active bonds. This type of metal–ligand cooperation plays a key
role in the recently discovered environmentally benign reactions
of alcohols, which are catalyzed by PNP and PNN pincer complexes
of ruthenium, including hydrogenation, oxidative dehydrogena-
tion, dehydrogenative coupling reactions, and water splitting [15].
Unfortunately, this metal–ligand cooperation is not present in case
of the benzene analog.
124 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152
Scheme 25. Synthesis of chiral PCP pincer ligand.
Scheme 26. General procedure for the synthesis of phebox.
2.3.1. Symmetrical pincer ligands
Like PNP, symmetrical PCP pincers with dibenzylic spacers
were synthesized via SN2 nucleophilic substitution of 1,3-
bis(halomethyl)benzene by dialkyphosphines in the presence of
triethylamine as a base, or together with direct substitution by R2 P−
[140–142] (Scheme 23). In addition, unsymmetrical PCP pincer lig-
ands and chiral PCP pincer ligands with substituted CH(R) benzyl
arms or mixed PRR groups have been described. The use of the
di-Grignard 1,3-C6 H4 (CH2 MgCl)2 in the synthesis of PCP ligands
was introduced recently by Milstein and Van Koten [143]. Simi-
larly, nucleophilic substitution of the 2,6-bis halomethyl benzene
with secondary amines generates the corresponding NCN pincer
ligand. The N,N,N,N-tetra methyl bis amino methyl benzene analog
can be prepared via methylation of ␣,␣ ,-diamino-m-xylene using
a mixture of formic acid and formaldehyde [144] (Scheme 23).
The introduction of N- or C(NHC) donors into the pincer struc-
ture is sometimes cumbersome, but the “Click” reaction [145]
provides a simple and rapid method for making both at the same
time. Copper catalyzed azide alkyne cycloaddition (CuAAC) using
2,6-dialkynyl benzene and alkyl azide result in the formation of
2,6-bis(1,2,3-triazol-4-yl)benzene. The ligand created can be used
as the NCN pincer ligand directly [146], or it can be alkylated to gen-
erate the bis imidazolium salt for use as a source of the CNHC CCNHC
pincer, as shown in Scheme 24.
The chiral PCP pincer ligand 118 has been synthesized from
the chiral diol analog 116, which was produced by the asymmet-
ric reduction of 1,3-diacetylbenzene and then converted into the
borane-protected phosphine 117 by in situ tosylation withTs2 O,
followed by nucleophilic attack with LiPPh2 (BH3 ). Subsequently,
the borane-protected phosphine was recrystallized from EtOAc to
remove the meso compound. The BH3 groups were removed in an
efficient manner to produce the enantiomeric pure phosphine 118
(Scheme 25) [147,148].
Among the NCN pincer ligands, the bis(oxazolinyl)phenyl
(abbreviated as phebox) ligand [149], which comprises two chiral
oxazolines and a benzene backbone, is one of the most useful frame-
works for constructing chiral NCN pincer complexes and it has
received much attention. The resulting phebox metal complexes
can provide a C2-symmetric environment around the active metal
center [51,150,151]. These phebox pincers can be readily prepared
in two steps starting from isophthaloyl chloride: amide formation
with a chiral ␤-amino alcohol followed by oxazoline formation with
methanesulfonyl chloride (Scheme 26).
PCP ligands 123 with NH spacers were prepared by the treat-
ment of substituted 1,3-diaminobenzene with 2 equiv. R2 PCl in the
presence of NEt3 and/or n-BuLi to produce the PN CN P pincer ligand.
All of these ligands are air stable in the solid state and in oxygen-
free solutions (Scheme 27) [152]. The phosphinito PCP pincer ligand
Scheme 27. Synthesis of PN CN P pincer ligand.
with O-atom as spacers (1,3-bis(dialkyphosphinito) benzene) 125
has been prepared with a good yield from chlorodialkylphosphine
and resorcinol in THF under basic conditions [153,154]. In addition,
the PO CO P pincer ligand 128 with the 4- and 6-positions blocked off
was prepared by reacting 2-methylresorcinol with tert-butanol in
the presence of phosphoric acid to investigate the C H activation
of the methyl group by ruthenium(II) salts [155] (Scheme 28).
Furthermore, 1,3-di-N-imidazolyl benzene can be used as start-
ing compound for preparing the bis(imidazolium) salts, which
are precursors of the symmetrical CNHC CCNHC pincer ligands.
Akabane et al. reported the synthesis of 1,3-di-N-imidazolyl
benzene starting from 1,3-diaminobenzene, involving four steps
[156]. Recently, Vargas described the high-yield one-step synthe-
sis of 1,3-di-N-imidazolylbenzene based on a copper-catalyzed
N-arylation procedure for nitrogen heterocycles. A solution of 1,3-
dibromobenzene and imidazole was heated in the presence of
copper oxide and potassium carbonate, followed by reaction with
various alkyl halides in toluene or solvent-free conditions to obtain
the bis(imidazolium) salt [157]. Subsequently, various copper pro-
cedures have applied been to catalyze N-arylation of nitrogen
heterocycles using aryl iodide and bromide [158–165] (Scheme 29).
2.4. Miscellaneous pincer ligands
In contrast to the most common classes of PCsp3 P pincer
ligands, the synthesis of the dibenzobarrelene-based PCsp3 P pin-
cer complexes reported by Gelman et al. is very simple using
the reliable Diels–Alder cycloaddition method. Facile access to
a readily modifiable platform also allows the tailoring of their
steric and electronic properties. Moreover, the rigidity of the
almost full-aromatic frame and lack of labile ␣- and ␤-hydrogens
translates into robustness and conformational stability, as well
as s-donation of the metallated bridgehead sp3 hybridized car-
bon. The unique topology of dibenzobarrelene molecules may be
utilized to design chiral-at-frame pincer ligands, which provide
a more efficient chiral pocket compared with more conven-
tional systems [166]. Despite their structural complexity, the
synthesis of these ligands can be accomplished readily using
a reliable and straightforward Diels–Alder cycloaddition strat-
egy. Thus, refluxing 1,8-bis-(diphenylphosphino)anthracene and
dimethyl fumarate in xylene overnight in a nitrogen atmosphere,
followed by reduction of the diester adduct with LiAlH4 in THF
yields the dibenzobarrelene-based pincer ligand [167].
 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152 125

Scheme 28. Synthesis of PO CO P pincer ligand.

Scheme 29. Synthesis of CCC pincer ligand with bis(imidazolium) salts.

Scheme 30. Synthesis of dibenzobarrelene-based PCsp3 P pincer and enantiopure PCS pincer ligands.

Given the general interest in the synthesis of more struc- the direct bromomethylation of acridine with bromomethyl-
turally complex chiral pincer ligands and the beneficial activities of methylether (BMME), and by reacting with the secondary
dibenzobarrelene-based ligands during chemical transformations phosphine HPiPr2 to obtain a good yield [168] (Scheme 31).
where the development of enantioselective versions is of great Silyl ligands have a strong -donating character and they have a
interest, Gelman et al. described a straightforward synthetic route stronger trans-influence than the other ligands used commonly in
for producing a new family of chiral nonracemic dibenzobarrelene- transition metal chemistry. Silyl ligands provide an electron-rich
based pincer ligands. The target molecules were synthesized via
lithiation of the racemic 1-bromo-8-diphenylphosphinotriptycene
137 and subsequent quenching with diastereomerically pure
(1R,2S,5R)-(e)-menthyl (S)-p-toluenesulfinate. The resulting mix-
ture of diastereomers was resolved using conventional column
chromatography. Hydrogenation of the diastereomerically pure
compounds led to the formation of enantiopure PCS pincer ligands
(Scheme 30).
In 2008, Gunanathan and Milstein reported an acridine-based
pincer ligand. This ligand was prepared from 4,5-bis(bromo-
methyl)acridine, which was obtained in a one-step reaction via Scheme 31. Straightforward synthesis of PNP acridine-based pincer.
126 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152

Scheme 32. Synthesis of symmetrical (PSiP) and unsymmetrical (PSiN) silyl pincer ligand.

Scheme 33. Synthesis of phosphinodi(benzylsilane) pincer ligand.

Scheme 34. Synthesis of PCP pincer ligand based on NHC.

metal center and coordinatively unsaturated species due to their
strong trans-labilizing effect. Therefore, “ancillary” silyl ligands
may provide transition metal complexes with unique reactivi-
ties that are useful for catalysis. Simple silyl ligands usually have
high reactivity and they cannot remain on transition metals as
“ancillary” ligands. The incorporation of a silyl group in a multi-
dentate ligand framework may be a useful strategy for producing
suitable “ancillary” silyl ligands. The very simple synthesis of
the symmetrical PSiP-pincer ligand 144 involved the lithiation
of (2-bromophenyl)dicyclohexylphosphine followed by coupling
with dichloro(methyl)silane to obtain the PSiP pincer ligand
[169]. The unsymmetrical analog PSiN 147 was also synthesized
in the same manner by the lithiation of (2-bromophenyl)di-
tert-butylphosphine and treatment with [2-(NMe2 )C6 H4 ]SiMeHCl,
where the former was prepared by reacting [2-(NMe2 )C6 H4 ]MgBr
with excess MeSiHCl2 (Scheme 32) [170]. The presence of two Si
atoms in bis(silyl) systems facilitates the generation of specific
properties with major effects in catalysis [171], where the SiCSi
ligand has a stronger -donor capacity than analogous PIII pincer
species. In this context, the synthesis of silicon pincer-type ligands
with Si H bonds that have “cooperating” effects may be highly sig-
nificant, thus phosphinodi(benzylsilane) 150 was prepared with a
yield of 83% in a one-pot reaction by the dilithiation of PhP(o-tolyl)2
with n-BuLi in the presence of TMEDA, followed by the addition of
ClMe2 SiH [172] (Scheme 33).
Transition metal complexes with NHC ligands have been a hot
research area. The NHC-based pincer ligand, PCNHC P, has been
reported as a pincer ligand for ruthenium. The PCNHC P pincer
ligand, 1,3-bis(2-chloroethyl)-3H-imidazol-1-ium chloride, was
prepared starting from imidazole via a two-step procedure because
attempts to perform a one-pot reaction between imidazole and 1,2-
dichloroethane always resulted in an impure mixture. Thus, the
compound 1-(2-chloroethyl)-1H-imidazole was first synthesized
by a phase-transfer catalytic approach followed by reaction with
in situ generated KPPh2 in DMSO to produce 154 as an air-sensitive
white solid [173] (Scheme 34).
A neutral PCP pincer ligand containing a central carbene was
synthesized in a straightforward manner from readily available
materials, which undergoes double C H activation after treatment
with [(p-cymene)RuCl2 ]2 . First, dipyrromethane was prepared
from the Lewis acid-catalyzed condensation reaction between
paraformaldehyde and an excess of pyrrole. Subsequent depro-
tonation of dipyrromethane with excess NaH in THF followed by
the addition of 2 equiv. of iPr2 PCl generated the PCP pincer ligand
 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152 127

Fig. 6. Neutral PCP and anionic PNP and NNN pincer ligands. Scheme 36. Synthesis of [RuHCl(CO)(PNP)] pincer complex based on acridine.

155 (Fig. 6) [174]. Similarly, the anionic diarylamido phosphine

ligand [PNP] 156, which was first reported by Kaska as a pincer
ligand for rhodium [175], has also been used as a pincer ligand for
RPCs [176–178]. Phosphines are generally “soft” donors whereas
amines are “hard” donors. Thus, substituting the two phosphine
donors of PNP pincer ligands with amines resulted in the formation
of a bis(amino)amido (N2 N) ligand, which maintained the struc-
tural rigidity and stability of PNP ligands, although it exhibited
different electronic properties and stabilized metals with higher
oxidation states. Hence, the bis(amino)amido (N2 NH) pincer,
bis[(2-dimethylamino)phenyl]amine (Me N2 NH) 157, was prepared
via the Pd-catalyzed C-N coupling of N,N-dimethylaminoaniline
with o-N,N-dimethylaminobromobenzene [179,180].

3. Synthesis of ruthenium pincer complexes

Scheme 37. Direct metallation of [Ru(COD)(metallyl)2 ] to PNP and PNN in the pres-
3.1. Direct metallation ence and absence of a hydrogen atmosphere.

After constructing the pincer ligand, its incorporate into the

pincer complex is another task. Direct metallation is the simplest
approach, but some important points should considered before the
synthesis process, such as the pincer ligand structure, ruthenium
source, reaction solvent, and other reaction conditions. In terms of
the pincer ligand structure, the donor sites should have unpaired
electrons that are available for bonding, which are derived from
heteroatoms or generated in situ from NHCs. Moreover, the steric
effect around the donor centers of the pincer ligand have a great
impact on the probability of bonding to the metal center, so the
alkyl/aryl groups around the donor sites are always a matter of con-
cern. The ease of substituting the ancillary ligands on the ruthenium
center also regulates the bonding process when producing the pin-
cer complex. Therefore, the most common ruthenium sources used
for direct metallation possess readily substituted triphenyl phos-
phine ligands. The synthesis of RPCs via direct metallation has been
reported using a variety of pincer ligands: PNP, PNN, PNS, NNN,
CNHC NN, and CNHC N CNHC , as well as diverse ruthenium sources,
and in combination with different solvents.
The electron-rich and bulky t-Bu-PNP ruthenium(II) pincer
complex 158 was prepared in a straightforward manner by the dis-
placement of PPh3 from the Ru(II) complex precursor. Heating a
THF solution of Ru(PPh3 )3 Cl2 with a stoichiometric amount of the
t-Bu-PNP 3t Bu2 at 65 ◦ C for 3 h in a nitrogen atmosphere yielded
the dinitrogen-bridged dimer complex 159, which appeared to
exist in equilibrium with its monomer 158 (Scheme 35), proba-
bly due of the steric hindrance of the bulky t-butyl groups of the
PNP ligand and the ease of substituting the triphenylphosphine
[181]. Attempts to synthesize the same complexes by alkene dis-
placement from the Ru(II) complex Ru(NBD)Cl2 or from the Ru(0)
complex Ru(COD)(COT) failed to yield the desired product. The eas-
ier reaction of the less bulky ligand iPr-PNP with RuHCl(PPh3 )3 (CO)
in THF at room temperature overnight resulted in the forma-
tion of [RuHCl(iPr-PNP)(CO)] 160 as an off-white solid [83]. The
acridine-based pincer complex 162 was prepared by reacting the
electron-rich tridentate PNP ligand with [RuHCl(PPh3 )3 (CO)] in two
different solvent systems [182,183] (Scheme 36).

Scheme 35. Synthesis of [Ru(II)(PNP)] pincer complexes by substituting the PPh3 ligand.
128 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152

Scheme 38. Dearomatization of PNP/PNN ruthenium pincer complexes.

Scheme 39. Synthesis of the Ru(PNS) pincer complexes and dimer formation.

Modification of the ruthenium precursor was used successfully
to obtain the bulky t-Bu-PNP pincer complex by olefin substitution.
Leitner reported the synthesis of a non-classical ruthenium hydride
pincer complex 164, which was obtained by heating the readily
available ruthenium source [Ru(COD)(2-methylallyl)2 ] with a PNP
ligand (2,6-bis((di-t-butylphosphino)methyl)pyridine) in pentane
with a hydrogen atmosphere (7 atm) [184–186]. Treatment of
the same ruthenium precursor with either the hemi-labile PNN or
the stronger PNP pincer ligand in the absence of a hydrogen atmo-
sphere also led to the in situ formation of [Ru(PNN)(2-methylallyl)2 ]
165a and [Ru(PNP)(2-methylallyl)2 ]165b [187], probably due to the
asymmetrically bonded allyl ligands (Scheme 37).
The hemilabile PNN pincer complex 166c was prepared in a sim-
ilar manner to the PNP analog 166a,b by refluxing the 3i Pr pincer
ligand with RuHCl(PPh3 )3 (CO) in THF. Deprotonation of complex
166a–c with KOtBu led to deprotonation of the benzylic phosphine
“arm,” instead of the hydride ligand to generate the dearomatized
complex 167a,b with a yield of 89% [83,188]. Similarly, the PNN
bipyridine based pincer 18 yielded the aromatized 168 and de-
aromatized pincer complexes 169 [189–191] (Scheme 38). Using
the same approach, the (PNS)RuH(Cl)CO complex 170 was prepared
by refluxing the PNS ligand with RuH(Cl)CO(PPh3 )3 in THF. How-
ever, attempts to synthesize the dearomatized (PNS)Ru(H)CO 171
using KOtBu or KHMDS as a base with a similar protocol to that

Scheme 40. Synthesis of PNN ruthenium pincer complexes based on 2,2 -bipyridinemethane and 2,2 -oxobispyridine and attempts at their dearomatization.
 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152 129

Fig. 7. Ruthenium pincer complexes reported by Gusev et al. based on simple pincer ligands.

reported for the preparation of the dearomatized PNP or PNN com-

plexes led to the formation of the symmetrical dimeric complex
172 (Scheme 39) [84].
Using the same approach, refluxing [RuHCl(CO)(PPh3 )3 ] with a
slight excess of the electron-rich PNN ligands 25a–c in THF yielded
the PNN-Ru complexes 173a–c. The dearomatized compounds
174a,b undergo cyclometallation to yield complexes 175a,b. For
cyclometallation to proceed, the coordination sphere around the
ruthenium center has to be rearranged, which depends on the Scheme 41. Microwave synthesis of PNN ruthenium pincer complex.
flexibility of the system, thus cyclometallation is qualitatively
faster with the dimethyl derivative 174a compared with the
spyrocyclopentyl derivative 174b. Cyclometallation also occurs
diastereoselectively and yields only one diastereomer of the
cyclometallated compounds. For the 2,2-oxobispyridine complex
173c, the dearomatized complex was too unstable to be isolated
(Scheme 40).
Gusev et al. reported the synthesis of a series of RPCs 176–178
(Fig. 7) that incorporated a simple pincer ligand, which could be
prepared on a large scale from inexpensive and readily available
starting materials, where they have high reactivity in many cat-
alytic applications [92,192–194]. The monohydride complexes can Scheme 42. Direct metallation of CNHC NN pincer ligand.
be prepared easily on a large scale with high yields by reacting
[RuHCl(CO)(PPh3 )3 /AsPh3 ] with the PNP or PNN pincer ligands via produced a quantitative yield of [RuCl2 (PPh2 )(dmso)PNN] complex
conventional PPh3 or AsPh3 ligand exchange. Further treatment 180 with sufficient purity [196] (Scheme 41).
of the monohydride 176a with KOtBu in ether with a hydrogen Direct metallation has also been extended to the syn-
atmosphere generated the dihydride trans-RuH2 (CO)(PNP) 176b thesis of CNHC NN RPCs via reacting the ruthenium source
[194], but the monohydride 177a failed to yields the dihydride [RuHCl(CO)(PPh3 )3 ] and the imidazolium salt in the presence of
analog and the dimeric structure was obtained instead [192]. The a strong base. This reaction was performed in two stages: the Ru(II)
dichloride complexes were prepared by reacting the pincer lig- precursor and CNHC NN ligand were refluxed overnight in THF to
ands with RuCl2 (CO)(DMF)(PPh3 )2 or RuCl2 (PPh3 )3 in glyme and achieve NN coordination, followed by the addition of a KHMDS
toluene, respectively, for 3–4 h. In the same manner, the ruthe- solution to complete the NHC moiety bonding. The resulting solu-
nium complexes 178a–d were obtained by conventional ligand tion was refluxed for another 2 h to obtain product 181 [197]
substitution reactions using HN-(C2 H4 SEt)2 with [RuCl2 (PPh3 )3 ], (Scheme 42).
[RuHCl(PPh3 )3 ], [RuCl2 (AsPh3 )3 ], and [RuHCl(CO)(PPh3 )3 ] respec- However, reacting the same Ru precursor with CNHC NN based
tively [195]. on bipyridine following the same protocol resulted in C H acti-
Interestingly, a PNN RPC has also been prepared using vation of the bipyridine moiety instead of direct metallation
microwave radiation instead of conventional heating, which to the N-atoms of the bipyridine, thus the bipyridine moiety
sometimes yields a significant amount of side products. Accord- remained non-coordinated (Scheme 43) [109]. The X-ray single
ingly, heating [Ru(dmso)4 Cl2 ] in THF at 120 ◦ C using microwaves crystal of the complex exhibited an octahedral structure with two
130 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152

Scheme 43. C H activation of a CNHC NN pincer based on bipyridine instead of direct metallation.
Reprinted with permission from ref. [109]. Copyright 2011 American Chemical Society.

phosphorus atoms located trans to each other, a hydride trans to

the NHC ligand, and CO trans to the C H-activated carbon of the
bipyridine ligand. A trial based on a one-pot reaction led to the
formation of an inseparable mixture of products.
The presence of bulky triphenylphosphine probably hinders the
coordination of the bipyridine ligand, thereby enforcing the C H
activation of the bipyridine moiety. Thus, changing the ruthenium
complex source into a phosphine-free precursor complex as Ru(p-
cymene)Cl2 (CO) with ligand 48 led to the formation of the desired
Fig. 8. Structure of the ruthenium(II) complex based on Me4 BPPy: correct structure
pincer complex (Scheme 44). Variable-temperature 1 H NMR mea- on the left and the originally reported structure on the right.
surements of the product in CD2 Cl2 proved that structures 184a
and 184b were in equilibrium with each other.
A CNHC NN RPC based on bipyridine-bearing triphenylphosphine
occupies three meridional sites and the two chlorides are mutu-
as an ancillary ligand was obtained in an effective manner by the
ally cis. Reaction of the Grubbs’ first-generation metathesis catalyst
coordination of [RuHCl(CO)(PPh3 )3 ] to the pre-generated free car-
analog with the free carbene 41a in THF yielded a mixture of
bene [109,198]. The free NHC ligand was generated by mixing the
products, by ligand exchange proceeded cleanly in toluene to gen-
CNHC NN pincer with LiHMDS in THF at −78 ◦ C, followed by warm-
erate a single product. Moreover, attempts to synthesize the less
ing to −30 ◦ C. Next, RuH(Cl)CO(PPh3 )3 was added and the mixture
bulky analogs of 191 by replacement of the di-isopropylphenyl sub-
was allowed to warm up slowly to room temperature. The reaction
stituents of the carbene ring with the smaller mesityl or t-Bu were
mixture was then refluxed overnight to obtain the pincer complex
unsuccessful, yielding complex mixtures [199].
185. Deprotonation of complex 185 with KHMDS in benzene or
In 2005, Wu et al. reported the first X-ray crystal structure
toluene resulted in the formation of the dearomatized complex
of a neutral ruthenium(II) complex based on 2,6-bis(3,5-
186, which was slightly unstable at room temperature (Scheme 45).
dimethylpyrazol-1-yl)pyridine (Me4 BPPy) (Fig. 8) [200]. Single
Using the same approach, Wright et al. reported the synthesis of
crystal analysis showed that the two chloride atoms were perpen-
CNHC NN based on bipyridine without a spacer via the in situ gen-
dicular to each other and one was trans to PPh3 . Based on their
eration of the free carbene 188 using KHMDS, followed by direct
results, they were able to correct the mistaken structure reported
reaction with Grubbs’ first-generation metathesis catalyst analog
previously [117]. RuCl2 (PPh3 )(Me4 BPPy) has been prepared via
to generate compound 189 (Scheme 46) [199].
direct metallation by refluxing an ethanolic solution of Me4 BPPy
Several ruthenium complexes with poly-NHC ligands have been
with RuCl3 ·3H2 O to obtain RuCl2 (Me4 BPPy), followed by reflux-
obtained starting from 2,6-pyridyl-bisimidazolium salts using dif-
ing with 1 equiv. of PPh3 in ethanol in the presence of excess Et3 N
ferent synthetic methodologies. The free carbene can be used in
[201,202].
mild and clean ligand substitution reactions in polar nonprotic
Since the first reported X-ray crystal structure of Ru(II) pin-
solvents, thereby providing high yields of pincer bis-carbene com-
cer complexes based on Me4 BPPy, the design and synthesis of
plexes. Reaction of 1 equiv. of the free carbene 41 with RuCl2 (PPh3 )3
Ru(II)NNN pincer complexes with unsymmetrical coordination
in THF yielded the ruthenium bis-carbene complex 190 as an
arms received more attention, because a metal complex that sus-
air-stable crystalline solid (Scheme 47) [103]. The X-ray single
tains a polydentate ligand with two unsymmetrical coordination
crystal analysis of compound 190 indicates that the pincer ligand
arms usually has a much higher catalytic activity due to the

Scheme 44. Direct metallation of Ru(p-cymene)Cl2 (CO) to a bipyridine-based CNHC NN pincer.

 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152
Scheme 45. Synthesis of the CNHC NN ruthenium pincer complex based on bipyridine with triphenylphosphine as an ancillary ligand via direct metallation to free carbene.
Scheme 46. In situ generation of a free carbene-containing CNHC NN pincer and metallation with Grubbs’ first-generation catalyst analog.
hemi-labile character of one of the ligand arms. A common
method for the synthesis of a Ru(NNN) pincer complex is
based on the reaction of the NNN tridentate pincer ligand
with 1.0 equiv. of RuCl2 (PPh3 )3 in refluxing toluene for 2–10 h
[55,112,121,123,124,200,203].
Thus reaction of ligands 61 and 62 with 1.0 equiv. of
RuCl2 (PPh3 )3 in toluene yielded the corresponding Ru(II)pincer
complexes. A pronounced advantage of complexes 194 and 196 is
that the ligand can be varied by treatment with NaHCO3 to gen-
erate the 16-electron complex, which is followed by treatment
with the ligand source in order to fine tune the activity of the pin-
cer complex (Scheme 48) [48,121,122]. RPCs based on the protic
2,6-di(1H-pyrazol-3-yl)pyridines ligand have also been reported,
where pincer ligand 199a,b with two butylpyrazole arms reacted
in a smooth manner with [RuCl2 (PPh3 )3 ] to yield the cationic
bis(pyrazole) complex 200a,b (Scheme 49) [204,205]. Interest-
ingly, treatment of the same ruthenium source in similar reaction
conditions with ligand 199c, but without any substituent at the 5-
position of the flanking pyrazole, yielded the dinuclear complex
201, where two ruthenium atoms were bridged by two ligands
with an unintended tautomeric form, probably to reduce steric hin-
drance around the nitrogen atoms distal to the central pyridine
[205].
Scheme 47. Synthesis of CNHC NCNHC ruthenium pincer complexes (poly-NHC ruthe-
nium complexes) via direct coordination to free carbenes.
131
The synthesis of ruthenium(II) NNN complexes 202, 203 con-
taining a chiral pyrazolyl–pyridyl–oxazolinyl ligand was achieved
in a similar manner (Scheme 50). Remarkably, pincer ligands 66a
and 66b both resulted in the formation of the same pincer com-
plex structure, whereas different structures were obtained with
pincer ligands 69a,b, depending on the substituent on the oxazo-
line moiety. The X-ray single crystal analysis of compound 203a
showed that the complex exhibits a neutral molecular structure
with a nearly planar tridentate NNN ligand, where the ruthe-
nium atom is surrounded by one PPh3 ligand, three N donor
atoms, and two chloride atoms. The PPh3 ligand is positioned
trans to the isopropyl group to reduce steric hindrance (Fig. 9)
[124].
Recently, Zhengkun et al. reported that reacting equimolar
amounts of ligands 76 and 77 with RuCl2 (PPh3 )3 in refluxing
2-propanol led to the formation of an ionic ruthenium(II) com-
plex bearing a pyridyl-based benzimidazolyl–benzotriazolyl pincer
ligand. The X-ray crystallography of complex 204a showed that the
cationic metal center is surrounded by the tridentate NNN ligand,
two PPh3 ligands, and a chloride anion in a distorted-bipyramidal
environment, with another dissociated chloride anion located in
the vicinity (Fig. 9). Further treatment of complex 204a with K2 CO3
in DCM yielded the neutral Ru(II) complex 205 via liberation of
1 equiv. of HCl. By contrast, treatment with K2 CO3 in isopropanol at
reflux temperature generated the RuH pincer complex 206, which
could also be obtained from 205 in the same manner (Scheme 51)
[125].
Milstein et al. reported the synthesis of a series of ruthe-
nium pincers complexes based on phosphinite pincer ligands
of the PO NO P type. Different ruthenium sources have been
used to synthesize various PO NO P pincers complexes, depend-
ing on the ruthenium source used. Heating the phosphinite
pincer ligand iPr-PO NO P with HRu(Cl)(CO)(PPh3 )3 in benzene
or THF at 80 ◦ C led to the formation of pincer complex (iPr-
PO NO P)Ru(H)(Cl)(CO) 207. By contrast, treatment of the iPr-PONOP
pincer with HRu(Cl)(PPh3 )3 in the same conditions yielded (iPr-
PONOP)Ru(H)(Cl)(PPh3 )3 208 after 30 min. Treatment of complex
208 with NaHBEt3 at −35 ◦ C immediately generated the trans-
dihydride complex (iPr-PONOP)Ru(H)2 (PPh3 ) 209. It should be
noted that the trans-dihydride complex can also be prepared by
a one-step reaction with RuH2 (PPh3 )4 using ligand 7b, but the iso-
lation of the complex from free PPh3 is a disadvantage of the latter
procedure (Scheme 52) [73].
132 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152

Scheme 48. Synthesis of [Ru(II)NNN] pincer complexes and their simple fine tuning.

Scheme 49. Synthesis of Ru(II)NNN pincer complexes with two proton-responsive pyrazole arms.

Scheme 50. Synthesis of Ru(II)NNN pincer complexes bearing a chiral pyrazolyl–pyridyl–oxazolinyl ligand.

The reaction of RuCl2 (PPh3 )3 with an equivalent amount of the
corresponding PN NN P ligands 9a–f in DCM yielded the PN NN P pin-
cer complexes via triphenylphosphine exchange [75]. However,
all attempts to prepare [Ru(tBu-PNP)(PPh3 )Cl2 ] were unsuccess-
ful, probably due to the presence of the sterically hindering tBu
groups and chloro ligand in the coordination sphere. The com-
plexes 210 are yellow to brown solids, which are stable in both
the solid state and in oxygen-free solutions. Because of the merid-
ional coordination mode of the PN NN P ligands and the rigidity
of the -NHPR2 substituents, the complexes can only form two
mer-stereoisomers with either trans- or cis-dichloro arrangements.
Their mixtures have not been detected based on 1 H NMR spec-
troscopy. Based on the X-ray crystallography of 210d, the geometry
around ruthenium can be referred to as a distorted octahedron with
a meridional PNP ligand, a PPh3 ligand cis to the pyridine nitro-
gen atom, and, remarkably, two mutually cis Cl atoms (Fig. 10).
However, changing the ruthenium source for [RuHCl(PPh3 )3 CO]
successfully generated a ruthenium complex bearing bulky tert
butyl groups [RuHCl(t Bu-PNP)CO] [206]. Thus, refluxing the PN NN P
9t Bu ligand with RuHCl(PPh3 )3 (CO) in THF for 12 h yielded the
Ru(II) complex 211 as a pale yellow solid, which readily under-
goes dearomatization after treatment with 1 equiv. of KOtBu in
 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152 133

Fig. 9. Solid state structures of some Ru(NNN)pincer complexes.

Copyright © 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim for 203a,b. Reprinted with permission from ref [125] for 204. Copyright 2013 American Chemical Society.

Scheme 51. Synthesis of ruthenium(II) pyridyl-benzimidazolyl–benzotriazolyl pincer complexes.

Fig. 10. Molecular structure of the complexes 210d [cis-Ru(PNP-BIPOL)(PPh3 )Cl2 ] on the left and 213 [Ru(PNNNP)CO]+ on the right.
Reprinted with permission from ref. [75]. Copyright 2006 American Chemical Society for 210d. Reprinted with permission from ref. [206] for 213. Copyright 2012 Elsevier.

THF, thereby resulting in an immediate color change from orange
to carmine. It should be noted that reacted complex 212 with
1.5 equiv. of formic acid results in rearomatization (Scheme 53). X-
ray crystallographic analysis of complex 213 detecetd a distorted
square-pyramidal geometry around the ruthenium center, with
the CO ligand trans to the pyridine nitrogen atom and the hydride
located in the apical position (Fig. 10). In the same manner, reaction
of the pincer ligands 134a,b with Ru HCl(PPh3 )3 (CO) in reflux-
ing THF resulted in the formation of hydrido chloro-RPCs, which
also yielded the dearomatized form after treatment with KOtBu
(Scheme 54) [93,94].
3.2. C H bond activation
The pincer PCSP 2 P undergoes C H activation using the common
ruthenium precursors, e.g., RuCl3 ·3H2 O, [RuCl2 -(COD)]n , [RuCl2 (p-
cymene)]2 [140], RuCl2 (PPh3 )3 [207], and [RuHCl(CO)(PPh3 )3 ],
in the presence of a base to yield the PCP RPCs. However,
134 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152

Scheme 55. CSp 2–H and CSp 3–H activation of PO CO P pincer ligand using
[RuHCl(CO)(PPh3 )3 ].

Scheme 52. Synthesis of dihydride ruthenium(II) and complexes based on a phos-

phinite PONOP pincer ligand.
[RuCl2 (COD)]n is the most fruitful source for this type of pin-
cer construction, which involves C H activation of the phenyl
group and NHCs. The reaction requires harsh conditions, i.e.,
a long reaction time and high temperature (170–190 ◦ C), so
ethylene glycol is typically used as the reaction solvent. Reac-
ting RuCl2 (PPh3 )3 with the PCP pincer ligand also results in
the C C or C H activation of Ar-CH3 , depending on the basic
medium [142]. The reaction of the phosphinite PCP ligand
[C6 H4 -1,3-(OPPh2 )2 ] with [(p-cymene)RuCl2 ]2 yields the bimetal-
lic species [208], but careful selection of the ruthenium source
and reaction conditions can direct the reaction toward the
desired orthometallated POCOP pincer complexes. Thus, reflux-
ing [RuHCl(CO)(PPh3 )3 ] with resorcinol bis(phosphinite) pincer
ligands 125a–d in toluene yielded the complexes 216a–d with
the general formula [RuCl(PCP)(CO)(PPh3 )]. Similarly, treatment of
[RuCl2 (PPh3 )3 ] with resorcinol bis(phosphinite) ligands generated
complexes of the [RuCl(PCP)(PPh3 )] type. Interestingly, a 2-methyl
C H activation occurred when C6 H-2-Me-4,6-t Bu2 -1,3-(OPPh2 )
128b was treated with [RuHCl(CO)(PPh3 )3 ], thereby generating
PCP–pincer complex 217 (Scheme 55) [155].
Bis(oxazolinyl)phenyl ligands (abbreviated as Phebox) provides
a C2 -symmetric and meridional configuration, as well as forming
a central stronger covalent bond with the metal compared with
bis(oxazolinyl)pyridine ligands (Pybox). The synthesis of ruthe-
nium complexes with the bis(oxazolinyl)phenyl moiety via C H
activation was reported using commercially available ruthenium
chloride in the presence of zinc powder [209], where a 4,6-
dimethyl derivative of the chiral 1,3-bis(oxazolinyl)benzene was
applied so that the dimethyl substitution at 4- and 6-positions
could prevent undesirable metallation by C H bond activation.
Simple refluxing of a mixture of RuCl3 ·3H2 O and 121a,b in EtOH

Scheme 53. Synthesis of PN NN P ruthenium pincer complexes and their reversible dearomatization-aromatization.

Scheme 54. Synthesis of RuPN NC N pincer complexes.

 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152
Scheme 56. Synthesis of bis(oxazolinyl)phenyl–ruthenium(II) pincer complexes via C H bond activation with RuCl3 ·3H2 O in the presence of Zn and Mg metals.
with Et3 N resulted in the formation of non-isolable ruthenium
complexes. In addition, the use of dimeric ruthenium sources,
[RuCl2 (COD)]2 and [RuCl2 (C6 H6 )]2 , failed to generate the desired
products. However, using zinc powder in the presence of COD with
RuCl3 ·3H2 O and 121a,b successfully generated a ruthenium(II)
complex with a yield of 65%, which had the dimeric structure
of [(Phebox-ipr)Ru(CO)Cl]2 -(ZnCl2 ) 218a,b. The dimeric complex
was then treated with sodium acetate or sodium acetylaceton-
ate at room temperature for 12 h to produce (Phebox-i pr)Ru(CO)
(acetate)/(acac) 219a,b and 220a,b, respectively, with good yields
(Scheme 56) [210–213]. The X-ray analysis of complex 220a
showed that the Ru center had a distorted octahedral geometry
with a meridionally coordinated Phebox ligand and a bidentate
acetylacetonato ligand. The CO ligand was perpendicular to the
Phebox plane. In addition, treatment of the Phebox ligand 121a
with the same ruthenium precursor in the same conditions, where
zinc metal was replaced with magnesium, successfully generated
[RuCOCl(Phebox)(H2 O)] 221 [212].
The harsh conditions require to prepare a free NHC ligand
may degrade the ligand, thus transmetallation has shown to be a
favorable procedure for obtaining NHC transition–metal complexes
[214]. However, treatment of the silver complex of imidazolium
iodide 56d with a stoichiometric amount of the most common
ruthenium sources, e.g., RuCl2 (PPh3 )3 or [Ru(p-cymene)Cl2 ]2 , in
DCM failed to generate the desired ruthenium(II)CNN complex.
Likewise, trials to generate the free carbene by treatment with
1 equiv. of base (KHMDS or NaH) in THF, followed by the addition
of RuCl2 (PPh3 )3 or [Ru(p-cymene)Cl2 ]2 , also failed to produce the
desired Ru(II) complex. Moreover, the one-pot reaction of CNHC NN
ligand 56d and RuCl2 (PPh3 )3 in the presence of a base did not pro-
duce the desired Ru(II) complexes. Interestingly, the CNHC NN pincer
ligand 56d reacts with an equivalent amount of RuCl3 ·3H2 O and
carbon monoxide in ethylene glycol at 190 ◦ C to generate the pincer
complex [Ru(CNN)Cl2 CO], where further treatment with KI yielded
the complex 222 and, in the same manner, the pincer ligand 52
produced the RPC 223 (Scheme 57) [110]. Using the same protocol,
Chung et al. reported the straightforward synthesis of CNHC NCNHC
RPC 224 by refluxing the CNC pincer ligand with ruthenium chlo-
ride in ethylene glycol for 4 h to yield the mer-isomer as the sole
product [215].
However, manipulating the ruthenium source into the dimeric
[(COD)RuCl2 ]n can complete the reaction process and generate the
anticipated product in milder conditions. Thus, the direct reaction
of [(COD)RuCl2 ]n and 2,6-bis(1-n-butylimidazolium-3-yl)pyridine
bromide in the presence of NEt3 and reflux with ethanol yielded the
135
Fig. 11. General strategies for constructing a chiral pincer complex.
ruthenium(II) CNC-pincer bis(carbene)complexes 225 [216]. The
use of NEt3 provides much better results for the deprotonation of
L compared with other mild (NaOAc, Na2 CO3 ) or stronger bases
(NaH, KOtBu) [216].
Activating the C H of the aromatic system with ruthenium
salts to synthesize pincer complexes that incorporate the strong
Ru C bond is of great interest. Baratta et al. presented a new CNN
framework for ruthenium-based pincer complexes that comprised
cyclometallated phenyl or benzoquinolinyl moieties, mainly via the
substitution of triphenylphosphine. Refluxing [RuCl2 (PPh3 )3 ] with
the CNN pincer ligand in isopropanol with a catalytic amount of tri-
ethylamine yielded thermally stable CNN pincer complexes via C H
activation and the substitution of PPh3 as well as the elimination
of HCl [135,137]. Similarly, complexes bearing the diphosphane
Ph2 P(CH2 )4 PPh2 (dppb) in conjugation with the CNN pincer ligand
were prepared by treating [RuCl2 (PPh3 )(dppb)] with the ligands 81,
96a (Scheme 58) [137,217].
There are two main strategies for constructing a chiral pin-
cer complex: the first method starts from a pincer ligand bearing
chiral centers located mainly in the arms, whereas the second
uses a chiral auxiliary ligand, as shown in Fig. 11. A series of the
chiral RPCs that contain the CNN pincer ligand have been devel-
oped using both strategies. The chiral complexes were prepared
by reacting [RuCl2 (PPh3 )3 ] with the appropriate chiral diphos-
phane using the pincer ligand (chiral/achiral) under reflux in
2-propanol (Scheme 59). It should be noted that the pincer com-
plex RuCl(CNN)(dppb) was also obtained by adding HCNN and dppb
to the ruthenium precursor [RuCl(␮-Cl)(␩6 -p-cymene)]2 in ethanol
under reflux, and in the presence of NEt3 , based on a one-pot syn-
thesis and without isolating the intermediate [137,218,219].
Alternatively, Ru(CNN) pincer catalysts can be synthesized
by reacting the HCNN pincer ligand and the commercially
136 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152

Scheme 57. Synthesis of [Ru(II)(CNHC NN)and CNHC NCNHC ] pincer complexes via direct C H bond activation.

Scheme 58. Synthesis of [Ru(II)(CNN)] pincer complexes via direct C H bond activation.

available [RuCl(-Cl)(6 -p-cymene)]2 to obtain both cationic and

Scheme 59. Synthesis of chiral Ru CNN pincer complexes.
neutral CNN cymene ruthenium complexes. Thus, treatment
of [RuCl(-Cl)(6 -p-cymene)]2 with 2 equiv. of 1-(6-arylpyridin-
2-yl)methanamine 81 in THF promptly coordinates the two
nitrogen atoms of the CNN ligand to form the [RuCl(6 -
p-cymene)(HCNN)]Cl complex 232. By contrast, the reaction
of 2-aminomethylbenzo[h]quinoline 96a with [RuCl(-Cl)(6 -p-
cymene)]2 leads to the formation of a neutral complex 234 due
to coordination to the N-atom of the amino group only. The
different behaviors of the two HCNN ligands can be ascribed
to the steric properties of the nitrogen ligands, where the
benzo[h]quinoline displays a higher rigidity and hinders the coor-
dination of the heterocyclic nitrogen to the Ru p-cymene moiety.
The cationic complex 232 reacts promptly with the monophos-
phine PPh3 in the presence of triethylamine in ethanol at reflux,
thereby yielding the pincer compound RuCl(CNNa )(PPh3 )2 233 via
displacement of p-cymene and ortho-metallation of the HCNN
ligand. In similar experimental conditions, 232 and 234 reacts
with the diphosphine Ph2 P(CH2 )4 PPh2 (dppb), thereby producing
the pincer catalysts RuCl(CNN)(dppb) 233 and 235 (Scheme 60)
[220].
 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152
Fig. 12. Series of cyclometallated ruthenium complexes with CCC and CNO pincer ligands.
In addition, the regioselective metallation of the 1-pyrenyl moi-
ety toward the ruthenium center has been investigated. Reacting
[Ru(PPh3 )3 Cl2 ] with 1-pyrenaldehyde-4-R-benzoylhydrazones
(H2 pnbhR, where R = H, Me, OMe, Cl and NO2 ) in the presence
of sodium acetate yielded ortho-metallated Ru(III)(CNO) pincer
complexes with the formula trans-[Ru(pnbhR)(PPh3 )2 Cl] 236
(Fig. 12) [221]. Similarly, ruthenium(III) pincer complexes have
been synthesized and characterized that incorporate a CNO pincer
ligand based on Schiff bases derived from 2-hydrazinopyridine
and 5-substituted salicylaldehyde [222]. A series of CCC-pincer
cyclo-metallated ruthenium complexes has also been synthe-
sized, primarily by treatment of the ruthenium source RuCl3 (L)
with AgOTf in acetone to replace the chloride atoms with
solvent molecules, where L = 4 -di-p-anisylamino-2,2 :6 ,2 -
terpyridine (daatpy), bis(N-methylbenzidazolyl)pyridine (Mebip),
4c 4-tolyl-2,2 :6 ,2 -terpyridine (ttpy), and trimethyl-4,4 ,4 -
tricarboxylate-2,2 :6 ,2 -terpyridine (Me3 tcbtpy), respectively.
Subsequently, these intermediates were treated with the known
bis-carbene precursor in the presence of KOtBu, followed by
anion exchange using KPF6 to obtain the desired cyclo-metallated
complexes 237 and 238 (Fig. 12) with moderate yields (21–49%).
X-ray analysis of the complex 237a showed that the ruthenium
metal had an octahedral configuration with the two imidazole
rings and the benzene ring was essentially coplanar [223].
Benzene-based CCC-RPCs with carbonyl group as an ancil-
lary ligand, 240a,b, were synthesized by heating 132a,b with
[Ru(COD)Cl2 ]n in ethylene glycol/EtOH (1:2) at 165 ◦ C in a sealed
Scheme 60. Synthesis of Ru CNN pincer complexes and the effects of the steric properties of the nitrogen ligands on coordination.
137
tube for 24 h. However, performing the reaction using more readily
accessible RuCl3 ·nH2 O in ethylene glycol or EtOH under the same
conditions obtained a substantially reduced yield (15%) [224]. It
was proposed that the CO source for the formation of 240a,b was
derived from the decarbonylation of alcohol, which was used as
the solvent [216]. The formation of these complexes might involve
the initial coordination of the NHC ligand to the ruthenium cen-
ter, followed by a sequence comprising the oxidative insertion
of phenylene–H and reductive elimination of the hydride. More-
over, treatment of the ruthenium complex [(CCC)Ru(CO)2 X] with
AgPF6 in CH3 CN at ambient temperatures resulted in the substi-
tution of the halide ligand with acetonitrile, which could also be
replaced by NN-bidentate, as shown in Scheme 61. X-ray structure
analyses showed that these complexes had pseudo-octahedral con-
figurations around the ruthenium center where the pincer ligand
occupied three meridional sites.
In general, the synthesis of [Ru(CNC/CCC)(NN)X] involves the
construction of the pincer complex, followed by the replacement
of two of the ancillary ligands with the bidentate NN ligand.
Alternatively, refluxing a ruthenium source that comprised NN
bidentate [Ru(NN)Cl4 ] 243 with pyridine-bridged bisimidazolium
or bis-benzimidazolium hexafluorophosphate 244 in ethylene gly-
col followed by reduction using Zn granules [225] yielded the
anticipated products. The chloride ligand can be substituted with
other ligands, e.g., CH3 CN and t-BuNC, by refluxing in acetonitrile
or t-butylonitrile in the presence of a silver salt (silver nitrate or
silver hexafluorophosphate) (Scheme 62).
138 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152

Scheme 61. Synthesis of ruthenium(II) carbonyl complexes with benzene-based CCC-pincer bis-carbene ligands.

Scheme 62. Synthesis of ruthenium(II) complexes bearing bipyridine and the N-heterocyclic carbene-based CNC pincer ligand.

Scheme 63. Synthesis of ruthenium pincer complexes via CSP 3 -H double activation.

Bulky pincer complexes of ruthenium based on a propane skele-
ton are capable of achieving C H activation and H-elimination
from the pincer ligand backbone to produce mixtures of olefin
and carbene products. Thus, reacting [RuCl2 (p-cymene)]2 with N,N-
bis(di-tert-butylphosphino)-1,3-diaminopropane yielded a mix-
ture of alkylidenes, Fischer carbenes, and olefin isomers of the
16-e monohydride, whereas the reaction with 1,3-bis(di-tert-
butylphosphinomethyl)cyclohexane 246 generated two olefin and
two alkylidene isomers of 16-e RuHCl[2,6-(CH2 PBut2 )], which all
resulted from dehydrogenation of the ligand backbone. However,
when the reaction was performed under hydrogen, the dihydride
products RuH2 Cl[2,6-(CH2 PBut2 )2 C6 H9 ] 247 were obtained. The
 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152
key intermediates associated with the C H activation reactions
were identified as 14-electron paramagnetic species RuCl(PCP),
which undergo hydrogenation to generate the 16-electron dihy-
drides, RuH2 Cl(PCP) [226]. In addition, the PCSP 3 P pincer ligand
that encompasses a central carbene undergoes double C H
activation. Heating a mixture of the PCP pincer ligand 155, [Ru(p-
cymene)Cl2 ]2 , and triethylamine for 12 h in toluene resulted in the
formation of the Ru(H)(Cl)(PCP) pincer complex as a reddish solid
with a yield of 75% (Scheme 63). Interestingly, exposure of this type
of carbene complex to strongly coordinating ligands such as CO
induced a quantitative 1,2-H shift [174].
Recently [227], Musa et al. reported the synthesis of an air-stable
ruthenium complex bearing the dibenzobarrelene-based cooper-
ating ligand. This complex was prepared via CSP 3 -H activation
by reacting the bifunctional ligand with the ruthenium precur-
sor Ru2 Cl4 (CO)6 in chloroform at room temperature. Analysis of
the reaction mixture by 31 P NMR indicated the presence of three
isomers of the target compound with a ratio of 1:0.3:0.14, which
appear to differ at the chloride ligand position. Moreover, X-ray
crystallographic analysis confirmed that the ruthenium center was
slightly distorted from the octahedral geometry because the com-
plex contained the dibenzobarrelene-based ligand with a high
degree of bend (Fig. 13).
3.3. Si H bond activation
Silyl ligands have a strong ␴-donating character and a stronger
trans influence than the ligands that are used commonly in tran-
sition metal chemistry [228]. Thus, silyl ligands may produce an
electron-rich metal center and coordinatively unsaturated species
due to their strong trans-labilizing effect. However, simple silyl lig-
ands usually have high reactivity and cannot remain on transition
metals as “ancillary” ligands. The incorporation of a silyl group in a
multidentate ligand framework may be a useful strategy for making
“ancillary” silyl ligands. Two methods can be used to incorporate
silyl ligands into the ruthenium pincer structure: (1) incorpora-
tion of one silyl group at the center of a multidentate framework
[169], and (2) attachment of two silyl groups in a rigid multidentate
framework [172].
RPCs have been prepared via Si–H activation using a variety
of ruthenium sources and pincer ligands. For example, ter-
tiary silane, [PSiP]H, was treated with an equimolar amount
of [RuCl2 (COD)] in dry THF with an ambient temperature in
the presence of NEt3 and oxidative addition of the Si H bond
to the ruthenium(II) center occurred, which was followed by
reductive-elimination to obtain Ru(PSiP) complex 250 with high
yields [169]. The phosphinodibenzylsilane compound also acts as
a pincer-type ligand. “PSi2 Hx ” can adopt different coordination
modes with ruthenium via diverse types of Si H bond activa-
tion. At room temperature, compound 150 reacts in deuterated
benzene/toluene, or THF, with bis(dihydrogen) RuH2 (H2 )2 (PCy3 )2
to yield compound 251 due to the formal substitution of two
dihydrogen and one tricyclohexylphosphine ligands in the ruthe-
nium source [RuH2 (H2 )2 (PCy3 )2 ] [172]. Attempts to synthesize
the (t Bu-PSiN-Me)Ru complex by reacting the PSiN pincer ligand
147 with common Ru(II) precursors, such as (PPh3 )3 RuCl2 and
[(p-cymene)RuCl2 ]2 , in the presence of Et3 N failed to yield the
anticipated products, and they typically led to the formation of mul-
tiple intractable products. By contrast, heating the pincer ligand
PSiN with 1 equiv. of (COD)Ru(2-methylallyl)2 for 18 h at 85 ◦ C
led to the formation of a single unpredicted product 253. How-
ever, the NMR features of product 253 were not consistent with
the formation of the (t Bu-PSiN-Me)Ru(2-methylallyl) complex.
Instead, the 1 H and 13 C NMR spectra indicated the formation of
a cyclooctenyl (PSiC)Ru carbene complex due to double C H bond
activation of a NMe group in the t Bu-PSiN-Me ligand and in the
139
1,5-cyclooctadiene, respectively. Finally, the structure of the prod-
uct was confirmed by X-ray crystallographic analysis (Scheme 64)
[170].
3.4. Transmetallation
Silver NHC complexes readily undergo exchange reactions
with binuclear halide-bridged metal complexes of rhodium and
ruthenium [229]. Transmetallation of the (NHC)CNN Ag(I) pincer
complex with a Ru(II) source in ambient conditions, the high yield,
and lack of a requirement for a strong base makes transmetallation
an attractive choice for the synthesis of RPCs. However, few RPCs
have been prepared via transmetallation from silver and lithium
intermediates due to the restriction of transmetallation to pincer
complexes that bear NHCs. During transmetallation, the silver or
lithium intermediates were treated with a halogenated ruthenium
precursor in DCM. The Ru(II) CNN 254 and CNC 256 pincer com-
plexes were prepared by in situ transmetallation using the silver
carbene complexes. In light-free conditions and at room temper-
ature, a solution of the pincer ligand solution in DCM was treated
with Ag2 O or the soluble precursor AgOC(CF3 )3 [230], which work
as both base and halide scavengers [108], followed by the addition
of [RuHCl(CO)(PPh3 )3 ] to obtain the product. The attempted de-
aromatization of the CNN pincer complex 254 with KOtBu yielded
the desired de-aromatized Ru(II)pincer complex 2255. By con-
trast, reacting the CNC pincer complex 256 with KOtBu in the
same conditions failed to yield the de-aromatized pincer com-
plex and the Ru(II) hydride complex 257 was formed instead
(Scheme 65). The deactivation and recovery of homogeneous cat-
alysts, as well as metal separation from the organic substrates, are
difficult challenges in homogenous catalysis. Ruthenium pincers
with a triethoxysilyl group have been immobilized on MCM-41
[108,231], MCM-41/Al, or MCM-41/Sn [232]. Supported complexes
have been prepared by refluxing a mixture of the pincer com-
plexes with a pendant silyloxy group and the support in toluene
for 16 h. The catalyst prepared in this manner had a metal loading
of 0.06 mmol of metal/g in the support, according to atomic absorp-
tion analysis. The activity and recyclability of the immobilized
catalyst were explored, which showed that the solid complexes
remained active and recyclable. Moreover, no deactivation was
observed after repeated recycling (Fig. 14).
Similarly, Suárez et al. reported the synthesis of Ru(II)CNC pincer
complexes 260a–d via a separable silver intermediate by treatment
of bis-imidazolium salts 258 with 1 equiv. of Ag2 O in CH2 Cl2 at
room temperature, thereby yielding the bimetallic silver complexes
259a–d, where further treatment with RuHCl(CO)(PPh3 )3 obtained
the product in the fac-coordination mode, probably because of
the steric hindrance of the bulky group on the imidazole ring
thus it cannot be considered as a pincer complex (Scheme 66).
Single-crystal X-ray diffraction of 260a (X = BF4 ) showed that
this complex comprised a distorted octahedral structure that
contained the CNC pincer coordinated in a fac configuration
(C2(NHC)–Ru–C2(NHC) = 101.3(8)◦ ), whereas the CO was located
trans to the pyridine nitrogen atom of the pincer system. Ini-
tial trials to synthesize the complex via direct metallation to
the free carbenes by reacting the imidazolium salt 258a (X = Br)
with different ruthenium precursors (RuHCl(PPh3 )3 , RuCl2 (PPh3 )3 ,
RuHCl(CO)(PPh3 )3 , and RuH2 (CO)(PPh3 )3 ) in the presence of a base
produced an inseparable mixture of products [233].
Transmetallation from silver intermediates was also extended
to the synthesis of phosphinated RPCs based on imidazole moiety.
The PCNHC P RPC 263 and 264 were prepared via transmetallation
of the silver complex 261. Treatment of PCNHC P·HCl with silver
oxide resulted in the formation of a trisilver complex containing
2 equiv., of PCNHC P ligand. Reacting the silver complex 261 with
RuCl2 (PPh3 )3 produced a bimetallic ruthenium(II)NHC complex
140 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152

Fig. 13. Synthesis of the dibenzobarrelene-based ruthenium pincer complex via CSP 3 -H activation.
Reprinted with permission from ref. [227]. Copyright 2013 American Chemical Society.

Scheme 64. Syntheses of ruthenium pincer complexes via Si H activation.

Scheme 65. Synthesis of ruthenium CNN and CNC pincer complexes via transmetallation from in situ generated silver complexes.
 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152 141

Fig. 14. Heterogenization of ruthenium CNN pincer complexes MCM-41, MCM-41/Al, or MCM-41/Sn.
Reprinted with permission from ref. [232]. Copyright 2012 Elsevier.

Scheme 66. Synthesis of Ru(CNC) pincer complexes via transmetallation from isolated silver complexes.

Scheme 67. Synthesis of ruthenium PCP pincer complex based on imidazole via silver transmetallation.

Scheme 68. Synthesis of ruthenium(N2 N) pincer complexes via lithium transmetallation.

142 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152
in the facial coordination and, interestingly, this fac-complex can
also be produced from a direct reaction between PCNHC P·HCl and
RuCl2 (PPh3 )3 without the need for a base, although this synthesis
is more complicated and less clean than the silver carbene trans-
fer reaction. After refluxing a solution of 262 in 1,2-dichloroethane
in a CO atmosphere, RuCl2 (CO)(PCNHC P) 263 was formed with an
octahedral geometry where the PCNHC P ligand was chelated in a
meridional fashion. Reduction of the ruthenium dihalide pincer
complex with excess NaBH4 in ethanol led to the isolation of the
ruthenium hydride RuHCl(CO)(PCNHC P) 267 (Scheme 67) [234].
Transmetallation from lithiated reagents has also been inves-
tigated in the preparation of RPCs. Lithiation of Me N2 NH 157
produced the dimeric lithium complex [(Me NN2 )Li]2 265, where the
structure was confirmed by X-ray crystallographic analysis. Treat-
ment of 265 with Ru(PPh3 )3 Cl2 at room temperature yielded the
[(Me N2 N)Ru(PPh3 )Cl] complex 266 (Scheme 68). X-ray crystallo-
graphic analysis showed that the Ru center was five-coordinated
and surrounded by the Me N2 N ligand, Cl anion, and PPh3 ligand in a
square-pyramidal environment, where the N2 N pincer ligand and
Cl anion comprised the plane, and the PPh3 ligand occupied an axial
position [235].
3.5. Trans-cyclometallation
Trans-cyclometallation refers to the exchange of cyclomet-
allated ligands at the metal center without the formation of
significant and detectable amounts of purely inorganic com-
pounds, as described by Van Koten in 2000 [236]. During
trans-cyclometallation, the relatively weakly coordinated ligand is
substituted by an incoming stronger bonding ligand, which also
involves aryl C H oxidative-addition/reductive-elimination. Thus,
the addition of a PCP ligand to the cyclometallated ruthenium pre-
cursor 268 is expected to result in the replacement of the hard
amine ligands by phosphine ligands, which are known to be much
softer ␦-donors. The development of the trans-cyclometallation
procedure addressed problems such as the presence of free phos-
phine or HCl, and the need for using chlorinated solvents, which
may give rise to secondary products. The pincer ligand 267a
was prepared in a trial of the functionalization of aryl ligands as
templates for incorporating catalytic active TM fragments onto
polymeric supports or well-defined carbosilane dendritic supports,
and treatment with the Ru(II) precursor RuCl2 (PPh3 )3 led to the
isolation of para-H complex 272 due to protodesilylation. The anal-
ogous complex RuCl[2,6-(Me2 NCH2 )2 C6 H3 ](PPh3 ) 268 reacts with
the ligand precursor 267a and generates the desired complex 270a
with an overall yield of 70% (Scheme 69) [237].
Refluxing the PCP pincer ligand with an NCN RPC resulted in
ligand exchange to form a PCP RPC, thereby releasing the free NCN
ligand [238,239]. The same method has been applied successfully
to ruthenation of “cartwheel” type ligand systems that contain six
potential metal-binding sites. Thus, refluxing 273 with 6 equiv. of
[RuCl(NCN)(PPh3 )] 268 in benzene for 20 h resulted in the forma-
tion of an air-sensitive hexakisruthenium complex where the color
changed from dark purple to dark green (Fig. 15) [240–242].
4. Effects of the pincer complex structure on the catalytic
activity
The primary role of the ligand in a catalyst complex is to sta-
bilize the transition metal in different oxidation states, thereby
accommodating the metal during the catalytic reaction. Pincer lig-
ands provide a good opportunity to blend three different or similar
coordination sites with the central metal, where each can have
a specific role in stabilizing different oxidation states. In addi-
tion to its strong coordination with the metal center, a pincer
ligand is a sterically and electronically tunable ligand that sup-
ports catalysis when coordinated with the usual catalytic active
metals. New pincer systems may even allow the emergence of
useful concepts that can gain general acceptance and aid the
design of molecular structures orientated toward a given prop-
erty. RPCs have various catalytic applications, e.g., hydrogenation
reactions [243] (direct and indirect), oxidative dehydrogenation
reactions [34] (acceptor and acceptorless), amination of alcohols
[168,244], hydrolysis of amines [245,246], hydroboration of termi-
nal alkynes [247], cyclopropanation of olefins [212], water splitting
[81], alkynylation of carbonyl compounds with terminal alkynes
[211,213], transesterification [248], olefin metathesis [199], and
alcohol racemization [249]. The fundamental differences between
various pincer classes result in dramatic variation in their reac-
tivities and catalytic properties. RPCs that catalyze hydrogenation,
oxidative dehydrogenation, and other catalytic applications are
controlled by many factors, in addition to the pincer ligand struc-
ture. Thus, knowledge of the main factors that affect these activities
and how to implement them in pincer ligands is essential for tuning
the pincer ligand to improve the performance of a catalyst.
4.1. Hemilability and non-innocent behavior of the pincer ligand
Hemilabile ligands are polydentate ligands that contain at least
two different types of chemical functionalities and they are capable
of binding to a metal center [250]. These functionalities are often
selected so that they are very different from each other to increase
the differentiation between their resulting interactions with the
metal center, and thus their reactivity and chemoselectivity. These
functionalities will influence the bonding/reactivity of the other
ligands that bind to the metal, particularly those in the trans posi-
tion. Combining hard and soft donors in the same ligand, which
is often called a hybrid or heteroditopic ligand, is a major goal
because it is hoped that different and contrasting chemistries may
be associated within the same molecule, thereby leading to novel
and unprecedented properties in the metal complexes obtained.
An essential feature of hemilabile ligands is the possession of at
least one substitutionable labile donor function, whereas the other
donor group(s) remains firmly bound to the metal center. The pres-
ence of a hemilabile ligand in a pincer complex may significantly
affect the reactivity of incoming substrates and promote transfor-
mations that would not occur otherwise (Tables 1 and 2). Examples
include the totally different behaviors of Milstein PNP and PNN
pincer complexes during the hydrogenation of esters and in
oxidative dehydrogenation reactions. Remarkably, the symmetri-
cal bis(di(tert-butyl)phosphinomethyl)-pyridine ligand (tBu-PNP)
exhibits very low activity in the hydrogenation of esters (Table 1,
entries 2 and 5), whereas the PNN analog has a much higher activity
with a major ligand effect that is attributable to the ligand hemil-
ability of the PNN pincer (Table 1, entries 3 and 6). The key features
that make this reaction successful are as follows. The ligand is hemi-
labile and it possesses a cooperative basic site in the ␤-position
relative to the metal (the deprotonated benzylic carbon). The basic
site allows the addition of H2 to the de-aromatized PNN complex,
thereby leading to the formation of the trans-dihydride complex,
while decoordination of the hemilabile amine arm facilitates the
binding of the ester substrate. Hydride transfer to the ester carbonyl
and the subsequent amine arm coordination and de-aromatization
of the pyridine core regenerate the complex, as well as eliminat-
ing a hemiacetal, which exist in equilibrium with the aldehyde in
solution. The aldehyde is then hydrogenated to the corresponding
alcohol via a similar cycle (Fig. 16) [188].
Similarly, during the acceptorless dehydrogenation of alco-
hols to carbonyl compounds with the PNP pincer complex 167b,
alcohols are converted into the corresponding ketones with the
liberation of dihydrogen. A significant improvement was achieved
 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152 143

Scheme 69. Synthesis of ruthenium PCP pincer complexes via trans-cyclometallation from Ru(II) NCN pincer complexes.

Fig. 15. Ruthenation of a “cartwheel” type ligand system via trans-cyclometallation.

when a ligand was constructed that combined hemilability and

cooperativity. Replacing one arm in the tridentate PNP ligand
with an aminomethyl group generated a PNN pincer ligand that
introduced hemilability due to the weaker binding of the amino

Scheme 70. Catalytic hydrogenation of carbonyl compounds with ruthenium pincer

complexes.

function. Modulating the donor sites and thus creating hemilabil-

Fig. 16. Proposed simplified catalytic cycle for the synthesis of esters, amides, and
imines from alcohols catalyzed by PNP and PNN RPCs (mechanisms that so not
involve amine arm dissociation are also possible).
ity in the pincer structure affected the catalytic activity as well as
controlling the reaction product. During the dehydrogenative cou-
pling of alcohols (or ester) and primary amines, the PNN pincer
complexes 165a [187,251] and 167c [49] promoted the formation
of amides, whereas the PNP analog 167b [50] led to imine for-
mation with the liberation of molecular hydrogen and water [50]
(Scheme 70).
The striking difference in the catalytic activity of the PNN and
PNP complexes can be rationalized as follows. For the PNN com-
plex with the hemilabile amine arm, the coordinated aldehyde
is attacked by the primary amine, thereby forming a quaternary
ammonium intermediate, which is followed by intramolecular pro-
ton transfer to the dearomatized phosphine arm. In the case of
the PNP complex, however, the attack on the aldehyde by the
amine occurs after it is released into solution, thereby generat-
ing a free hemiaminal intermediate that liberates water. Using the
144 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152

Table 1
Catalytic activities of different pincer complexes in direct hydrogenation reactions.

E Catalyst Substrate Reaction conditions Conv. (%) Ref

Cat. mol% PH2 (bar) T (◦ C) t (h) Base (mol%)

Cinnamaldehyde 0.5 40 30 20 B1 (1.0) 87

1 [196]
Cl
N PPh2
Ru 1,1 ,1 -trimethylacetophenone 0.5 50 50 20 B1 (1.0) 99
DMSO Isobutyrophenone 0.5 50 50 20 B1 (1.0) 99
N
H2 Cl Methyl heptafluorobutanoate 0.5 50 140 24 B2 (1.0) 100
180 Dimethyl-o-phthalate 0.5 60 150 60 B2 (1.5) 100

H Ethyl benzoate 1.0 5.3 115 16 – 7.5

2 Pi Pr 2 [188]

N Ru CO

PiPr 2
167a Ethyl benzoate 1.0 3.5 160 16 – 12

H Ethyl benzoate 1.0 5.3 115 4 – 99.2

Pi Pr 2 Hexyl hexanoate 1.0 5.3 115 5 – 82.2
Benzyl benzoate 1.0 5.3 115 7 – 98.5
N Ru CO Methyl benzoate 1.0 5.3 115 4 – 100
3 [188]
Ethyl butyrate 1.0 5.3 115 4 – 100
NEt 2 Ethyl acetate 1.0 5.3 115 12 – 86
Tert-butyl acetate 1.0 5.3 115 24 – 10.5
167d Dimethyl terephthalate 1.0 5.3 115 5 – 100

Ethyl benzoate 1.0 5.3 105 2 B1 (1.0) 99.6

N
4 H [197]
N Phenyl ethylacetate 1.0 5.3 105 2 B1 (8.0) 99.7
Ru N Methyl acetate 1.0 5.3 105 2 B1 (8.0) 96
N Ethyl acetate 1.0 5.3 105 2 B1 (8.0) 99
Br Benzyl acetate 1.0 5.3 105 3 B1 (8.0) 90
dipp CO Tert-butyl acetate 1.0 5.3 105 2 B1 (8.0) 93
275 Diethyl succinate 2.0 5.3 105 2 B1 (.08) 99

H Butyl butyrate 0.5 10 110 12 – 10

5 [263]
PtBu2
N Ru H
t H B H
P Bu2
H
276 Benzyl benzoate 0.5 10 110 12 – 17

H Hexyl hexanoate 0.5 10 110 12 – 94

6 PtBu2 [263]

N Ru H
NEt2 H B H
Butyl butyrate. 10 110 12 – 98
277 H Benzyl benzoate 10 110 12 – 99
Methyl benzoate 10 110 12 – 97

Ethyl benzoate 1.0 5.4 135 2 B1 (1.0) 97

N
H
N N [109]

7 Ru Mes Benzyl benzoate 5.4 135 2 B1 (1.0) 91

CO
N PPh Ethyl butyrate 5.4 135 2 B1 (1.0) 98
3
Pentyl pentanoate 5.4 135 2 B1 (1.0) 96
186 Glycolide 1.0 10 110 48 B1 (1.0) 58
Glycolide 10 110 48 – 0 [198]
l-lactide 50 110 12 B1 (1.0) 67
 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152 145

Table 1 (Continued)

E Catalyst Substrate Reaction conditions Conv. (%) Ref

◦
Cat. mol% PH2 (bar) T ( C) t (h) Base (mol%)

Glycolide 1.0 10 110 48 – 93

[198]

Glycolide 50 110 12 – 85
l-lactide 10 110 48 – 82
l-lactide 50 110 12 – 91
N-benzyl-2-methoxyacetamide 1.0 10 110 48 – 90
N-hexyl-2-methoxyacetamide 1.0 10 110 48 – 91
N-hexylfuran-2-carboxamide 1.0 10 110 48 – 69
N H P N-benzylbenzamide 1.0 10 110 48 – 57
N-ethyl acetamide 1.0 10 110 48 – 71
8 Ru N-methylpropionamide 1.0 10 110 48 – 68
N N-phenylacetamide 1.0 10 110 48 – 95
[189]

CO N-phenylhexanamide 1.0 10 110 48 – 92

N-phenylbenzamide 1.0 10 110 48 – 92
169
N-acetylmorphiline 1.0 10 110 48 – 98
N-formylmorpholine 1.0 10 110 48 – 98
2-methoxy-1-(pyrrolidin-1-yl)ethanone 1.0 10 110 48 – 97
Dimethyl carbonate 0.1 10 110 48 – 96
Dimethyl carbonate 0.2 50 110 14 – 89
Dimethyl carbonate 1.0 10 100 8 – >99
Methyl benzylcarbamate 1.0 10 110 48 – 97 [190]
Methyl pentylcarbamate 1.0 10 110 48 – 94
Methyl formate 0.06 10 110 48 – 96
Methyl formate 0.02 50 110 14 – 94

Dimethyl carbonate 0.04 40 110 3.5 – >99

9 [190]
N H P
Ru
Et2 N
CO
Dimethyl carbonate 0.04 60 110 1.0 – >99
167c Methyl formate 0.1 9 145 36 – >99

H Methyl benzoate 0.1 50 100 16 B3 (10) 98

H
N PPh 2 Methyl undecanoate 50 100 16 B3 (10) 98
10 [258]
Ru Dimethyl succinate 50 100 16 B3 (10) 100
Methyl 2-(benzyloxy)acetate 50 100 16 B3 (10) 100
P CO Methyl 2-(piperidin-1-yl)acetate 50 100 16 B3 (10) 100
Ph2
Methyl 3-methoxypropanoate 50 100 16 B3 (10) 11
Cl
Methyl 3-(N,N-Me2 )propanoate 50 100 16 B3 (10) <10
176c Isopropyl benzoate 50 100 16 B3 (10) 98
Tert-butyl benzoate 50 100 16 B3 (10) 96

H c Ethylene carbonate 0.1 50 140 0.5 B1 (1.0) 99

H
11 N PR 2 [264]
a Ethylene carbonate 0.1 50 140 0.5 B1 (1.0) 74
Ru
f Ethylene carbonate 0.1 50 140 0.5 B1 (1.0) 16
P CO g Ethylene carbonate 0.1 50 140 0.5 B1 (1.0) 76
R2
h Ethylene carbonate 0.1 50 140 0.5 B1 (1.0) 24
Cl 176
O
a; R=i Pr, c; R=Ph,
f; R=tBu, g; R=Cy, O O
R1 R3
h;R=1-Ad
R2 n R4
c n=0, 1 0.1 50 140 4–10 B1 (1.0) >99

H3C
N PPh2
Ru
P CO
Ph2
Cl
12 278 Ethylene carbonate 0.1 50 140 10 B1 (1.0) – [264]
146 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152

Table 1 (Continued)

E Catalyst Substrate Reaction conditions Conv. (%) Ref

◦
Cat. mol% PH2 (bar) T ( C) t (h) Base (mol%)

x a Methyl 2,2-difluoroacetate 0.02 10 40 6 B1 (25) >99

H PPh 2
N [265]
13
Ru
P CO
Ph2 x b Methyl 2,2-difluoroacetate 0.02 10 40 6 B1 (25) >99
a; X= H, Cl c Methyl 2,2-difluoroacetate 0.02 10 40 21 B1 (25) 65
b; X= H,H a Methyl 2,2,2-trifluoroacetate 0.05 25 40 24 B1 (25) 98
279a-c
c; X= Cl, Cl a Methyl acetate 0.02 10 40 18 B1 (25) 17
a Methyl 3,3,3-trifluoropropanoate 0.05 30 40 22 B1 (25) 5

i Pr
2H
P Co
Ru
N N
H
Cl
14 177a Methyl benzoate 0.05 50 100 1.7 B1 (1.0) 99 [192]

Ph 2 Cl Methyl benzoate 0.025 50 40 16 B4 (5.0) 98

P PPh 3 Ethyl acetate 0.005 50 40 16 B5 (1.0) 100
Ru Methyl hexanoate 0.005 50 40 18 B4 (5.0) 94
15 Methyl 2-methoxyacetate 0.025 50 40 16 B1 (1.0) 100 [92]
N N Methyl 2-hydroxypropanoate 0.05 50 40 16 B4 (10) 98
H N-benzylideneaniline 0.002 50 40 16 B1 (1.0) 100
Cl N-benzylidenepropan-1-amine 0.05 50 40 16 B1 (1.0) 100
177d
Methyl benzoate 0.025 50 40 6 B1 (1.0) 95
Ethyl benzoate 0.005 50 40 16 B5 (1.0) 85
Dimethyl phthalate 0.1 50 100 1.2 B4 (1.0) 96
Dimethyl isophthalate 0.05 50 40 16 B4 (1.0) 93
Dimethyl isophthalate 0.1 50 100 1 B4 (1.0) 100
Ethyl acetate 0.0025 50 40 14 B5 (1.0) 95
Ethyl acetate 0.0012 50 40 21 B5 (1.0) 73
Methyl hexanoate 0.005 50 40 24 B4 (1.0) 81
Et Cl Methyl 2-methoxyacetate 0.01 50 60 16 B4 (1.0) 100
S PPh3 Methyl 3-methoxypropanoate 0.05 50 23 21 B4 (1.0) 97
Tert-butyl acetate 0.025 50 100 1 B1 (1.0) 100
Ru Methyl non-3-enoate 0.05 50 40 8 B1 (1.0) 100
16 N SEt Methyl 2-hydroxypropanoate 0.05 50 100 1 B4 (1.0) 93 [195]
H Oxepan-2-one 0.01 50 100 2 B4 (1.0) 99
Cl N-benzylideneaniline 0.005 50 23 1.5 B1 (1.0) 100
N-(1-phenylethylidene)aniline 0.002 50 40 1 B4 (1.0) 63
178b N-(1-phenylethylidene)propan-1-amine 0.05 50 40 6 B1 (1.0) 100
Acetophenone 0.0025 50 40 24 B1 (1.0) 100
Cyclohexanone 0.005 50 23 1 B1 (1.0) 100
4-(tert-butyl)cyclohexanone 0.005 50 23 2 B1 (1.0) 100
2-pentanone 0.005 50 40 1 B1 (1.0) 100
Benzaldehyde 0.01 50 100 1.5 B4 (1.0) 94
Styrene 0.05 50 40 20 B1 (1.0) 100
1-pentene 0.05 50 40 4848 B4 (1.0) 75
2-pentene 0.05 50 40 B4 (1.0) 13

B1 : KOt Bu, B2 : LiHBEt3 , B3 : NaOMe, B4 : KOMe, B5 : NaOEt.

same approach, the dehydrogenative coupling of ␤-amino alcohols
generates pyrazines and peptide formation, which depend on the
presence or absence of the hemilabile arm. Thus, for the bulky PNP
complex 167b that lacks a hemilabile amine “arm,” dissociation of
the aldehyde and its attack by the amino alcohol occur in solution,
thereby yielding an imine (by water liberation from a hemiami-
nal), eventually producing a pyrazine after the aromatization of
a presumed 1,4-dihydropyrazine intermediate. For the hemilabile
PNN complex 167c, a sequence that involves nucleophilic attack
by the amine group of the second amino alcohol molecule on the
aldehyde, which is coordinated with the PNN complex, eventually
yields a peptide (Schemes 71 and 72) [252].
Ruthenium(II) complexes that incorporate the unsymmetrical
NNN pincer ligand exhibit an exceptionally high catalytic activity
for the transfer hydrogenation of ketones in refluxing isopropyl
alcohol compared with the symmetrical ligand, with final TOFs
of up to 7.2 × 105 h−1 that increase more than 100-fold in a few
seconds (Table 2, entries 3 and 4). The exceptionally high catalytic
activity of these complexes is also attributed to the hemilability of
the ligand and the ease of conversion from the saturated complex to
the coordinately unsaturated precatalyst in the reaction conditions.
Moreover, complexes that lack the NH functionality (Table 1, entry
12) have very low catalytic activities because the pincer ligand is
incapable of unsaturated precatalyst formation, thereby supporting
the principle of non-innocent ligand cooperation.
4.2. Flexibility of the pincer framework (aliphatic versus
aromatic)
RPCs exhibit unprecedented catalytic activity in both acceptor
and acceptorless dehydrogenation reactions [34]. In acceptorless
dehydrogenation reactions, the catalytic process has been proposed
 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152 147

Table 2
Catalytic activities of different pincer complexes in the transfer hydrogenation of carbonyl compounds.
O OH i OH
+ PrOH, Base
R1 R2 + CH3 COCH 3
R1 R2 .

E Catalyst Substrate Reaction conditions Conv. (%) Final TOF (×104 h−1 ) Ref.

H-donor Base T (◦ C) t (h)

i
NMe 2 Cyclohexanone PrOH KOH 82 3.3 98 0.11 [266]
PPh3
1
Ru Cl

i
NMe2 Acetophenone PrOH KOH 82 44 70 0.003
i
280 Benzophenone PrOH KOH 82 90 90 0.008
i
2-pentanone PrOH KOH 82 4.5 0.1
i
PPh 2 Cyclohexanone PrOH KOH 82 1.3 98 2.7 [266]
PPh 3
2 Ru OTf

PPh2 i
Acetophenone PrOH KOH 82 0.5 90 0.9
i
281 Benzophenone PrOH KOH 82 108 98 0.01
i
2-pentanone PrOH KOH 82 1.5 90 0.2
i i
Cyclohexanone PrOH PrOK 82 1/12 98 0.58 [200]

N N N
3 Cl
N N
Ru
i i
Ph3 P Acetophenone PrOH PrOK 82 1/12 96 0.57
i i
Cl Benzophenone PrOH PrOK 82 3 89 0.01
192 1-phenyl propanone i
PrOH i
PrOK 82 3 95 0.06
i i
1-chloroacetophenone PrOH PrOK 82 1/12 100 0.6
i i
2-chloroacetophenone PrOH PrOK 82 1/12 98 0.58

Cyclohexanone i
PrOH i
PrOK 82 2.7 × 10−3 98 70.5 [121]

4 N N
Cl
N N NH Acetophenone i
PrOH i
PrOK 82 16 × 10−3 95 11.4
Ru
Benzophenone i
PrOH i
PrOK 82 8.3 × 10−3 98 23.5
Ph 3P 1-phenyl propanone i
PrOH i
PrOK 82 16 × 10−3 98 11.7
Cl
1-chloroacetophenone i
PrOH i
PrOK 82 2.7 × 10−3 96 69.1
194 2-chloroacetophenone i
PrOH i
PrOK 82 2.7 × 10−3 95 22.8

H Cyclohexanone i
PrOH i
PrOK 82 2.7 × 10−3 100 72.5 [48,122]
N
N N
5 Cl
N N
Ru
Cyclohexanone i
PrOH i
PrOK 25 33 × 10−3 99 2.97
Ph3 P
Cl Acetophenone i
PrOH i
PrOK 82 2.7 × 10−3 98 70.5
Acetophenone i
PrOH i
PrOK 25 500 × 10−3 96 0.19
196a
Benzophenone i
PrOH i
PrOK 82 2.7 × 10−3 98 70.5
Benzophenone i
PrOH i
PrOK 25 250 × 10−3 97 0.38
i i
Cyclohexanone PrOH PrOK 82 1.5 100 0.03 [110]

t Bu N N
6 I
N N Ru N
H nBu i i
I CO Acetophenone PrOH PrOK 82 2.0 98 0.02
i i
223
1-phenyl propanone PrOH PrOK 82 2.0 98 0.02
i i
1-chloroacetophenone PrOH PrOK 82 12 98 0.004
i i
2-chloroacetophenone PrOH PrOK 82 0.5 98 0.09

Cyclohexanone i
PrOH i
PrOK 82 16 × 10−3 97 6.0 [135]

7 N N
PPh 3
N Acetophenone i
PrOH i
PrOK 82 16 × 10−3 98 5.88
Ru
Ph3 P 1-phenyl propanone i
PrOH i
PrOK 82 16 × 10−3 99 5.94
1-chloroacetophenone i
PrOH i
PrOK 82 16 × 10−3 99 5.94
Cl
2-Acetonaphthone i
PrOH i
PrOK 82 16 × 10−3 97 5.82
227
Benzophenone i
PrOH i
PrOK 33.3 × 10−3 98 2.94
i
Cyclohexanone PrOH – 40 16 99 – [93]

8 O
N N H
tBu
2P Ru N
Acetophenone i
PrOH – 40 16 74 –
i
CO 4-Bromoacetophenone PrOH – 40 10 97 –
i
215 1-Acetonaphthone PrOH – 40 5 93 –
i
3-Hexanone PrOH – 40 16 99 –
148 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152

Table 2 (Continued)

E Catalyst Substrate Reaction conditions Conv. (%) Final TOF (×104 h−1 ) Ref.
◦
H-donor Base T ( C) t (h)
i
Cyclohexanone PrOH – 82 16 100 – [206]

9
N N H NH
t Bu P Ru PtBu
2 Acetophenone i
PrOH – 82 16 83a –
CO 4-Bromoacetophenone i
PrOH – 82 16 94a –
i
212 2-Heptanone PrOH – 82 16 93 –

Acetophenone i
PrOH i
PrONa 82 83.3 × 10−3 98 93 [267]
Ph 2
10 P

N Ru
2-chlorooacetophenone i
PrOH i
PrONa 82 33.3 × 10−3 99 68
Cl P
Ph2 2-MeO-acetophenone i
PrOH i
PrONa 82 33.3 × 10−3 96 54
NH 2
t
Acetophenone b i
PrOH i
PrONa 82 66.6 × 10−3 98 66
Bu Acetophenone i
PrOH i
PrONa 82 83.3 × 10−3 98 110 [137,219,268]
282a,b
Cl Acetophenone i
PrOH i
PrONa 60 166 × 10−3 98 18 [136,218]
N
11 Ru
Ar 2P N
Cy 2P H
H
Fe 2,4-OMe2 -acetophenone i
PrOH i
PrONa 82 33.3 × 10−3 98 130
2-chlorooacetophenone i
PrOH i
PrONa 60 33.3 × 10−3 97 15
231b
2-acetyl pyridine i
PrOH i
PrONa 60 500 × 10−3 99 12
Ar= 4-MeO-3,5-Me 2C 6H 2
2-Acetonaphthone i
PrOH i
PrONa 60 83.3 × 10−3 97 20

Acetophenone, P = PPh3 i
PrOH NaOH 82 83.3 × 10−3 95 0.57 [269]

12 O O
N
Cl
N N
Ph Ru
Ph
P
Cl Acetophenone, P = Pi Pr3 i
PrOH NaOH 82 50 × 10−3 97 0.97
283 1-phenyl propanone, P = Pi Pr3 i
PrOH NaOH 82 83.3 × 10−3 97 0.58
P= PPh3, Pi Pr3 3-bromooacetophenone, P = Pi Pr3 i
PrOH NaOH 82 16.6 × 10−3 91 2.7c

Acetophenone, L = PMe3 i
PrOH NaOH 82 250 × 10−3 97 – [270]

13 O O
N
Cl
N N
iPr iPr Ru
Cl L
Acetophenone, L = CNBn i
PrOH NaOH 82 250 × 10−3 92 –
284 Acetophenone, L = CNCy i
PrOH NaOH 82 500 × 10−3 86 –
L= PMe3 , CNBn, CNCy, MeCN Acetophenone, L = MeCN i
PrOH NaOH 82 250 × 10−3 47 –
a
A mixture of alcohol and substituted styrene was obtained.
b
Catalyst prepared in situ from the pincer ligand and RuCl2 (PPh3 )(dppb).
c
TOF at t = 1 min.

to proceed via cooperative interactions among substrates with the

basic site of the pincer ligand and with the electrophilic metal.
A hydrogen acceptor is not necessary because the ligands play
an active role in the hydrogen abstraction and liberation process.

Scheme 72. Synthesis of peptides and pyrazines from ␤-amino alcohols via pincer
ligand-controlled selectivity.

Scheme 71. Dehydrogenative coupling of alcohols and amines into amides and
imines, depending on the hemilability of the pincer ligand.
However, the bulky ligands in these catalysts may hinder the abil-
ity of the substrate to interact with both sites in the complex,
which may explain why tertiary amides are difficult to synthe-
size via acceptorless dehydrogenation coupling of alcohol and
amines [49,253–255]. Various rigid RPCs have been produced based
on 2,6-disubstituted benzene and pyridine, but new members
of this family, including the complexes 176, 178, 278, and 279,
 H.A. Younus et al. / Coordination Chemistry Reviews 276 (2014) 112–152
have started to receive greater attention recently (Tables 1 and 2)
[92,192,194,256–259]. The flexibility of the pincer framework has
a significant impact on catalytic hydrogenation and acceptorless
dehydrogenation reactions may be attributed to the following:
(i) highly flexible pincer ligands support different coordination
geometries, thereby facilitating the mer-fac interconversion, which
might be involved in the catalytic cycle; (ii) the loss of the steric
effect in the central aromatic pyridine/benzene ring allows the
desired cooperative interactions between the substrates and the
metal/ligand framework [260,261]. Transition metal complexes
with sulfur ligands are active catalysts in a considerable number
of homogeneous reactions [262]. Therefore, replacing N- and P-
donors with softer S-donors, as well as the non-innocent behavior
and flexibility of the designed pincer ligand, can yield state-of-
the-art catalysts for use in hydrogenation and dehydrogenation
reactions (Table 1, entry 16) [195].
5. Conclusion and future prospects
Significant achievements have been made in the chemistry of
pincer-type complexes over the last decade. The wide variety of
applications of pincer type molecular structures is a direct indi-
cation of one of the ligands’ most attractive features, i.e., various
options for tuning their electronic and steric properties without
affecting the ligand’s ability to bind to the metal center. RPCs have
received much attention as some of the most important ruthenium
complexes. Various strategies have been presented for constructing
RPC skeletons but improving ligand design is almost an art. Sym-
metrical ligands are easy to produce, but unsymmetrical ligands are
receiving much attention for use as RPCs due to their hemilability
and outstanding catalytic applications. Pyridine-based RPCs have
been explored in depth for synthesis and many catalytic applica-
tions, but RPCs with other motifs remain relatively or completely
underdeveloped.
Various procedures have been reported for the synthesis of
RPCs, e.g., direct metallation, C/Si H bond activation, transmet-
allation, and trans-cyclometallation. Regardless of whether the
reaction occurs or not, many factors control the reaction prod-
uct, e.g., donor atoms, steric hindrance in the pincer ligand around
the donor atoms, the ability to displace the ligand in the ruthe-
nium source, and the reaction conditions. Direct metallation is used
widely because of its applicability to most pincer ligands based on
pyridine-bearing heteroatoms on both side arms, e.g., PNP, PNN,
PNS, PO NO P, PN NN P, PN NC N, and NNN. Numerous RPCs have been
synthesized via CSP 2 H bond activation, but only a few examples
have been reported based on CSP 3 H activation. RPCs have also
been prepared via Si H activation using a variety of ruthenium
sources and pincer ligands. Bulky groups around the donor atoms
have a great impact on the ability to form a complex and Si H acti-
vation might be facilitated by CSP 3 H activation. Transmetallation
from NHC-ligated Ag(I) complexes and lithiated reagents, as well
as trans-cyclometallation, have been utilized successfully for the
preparation of RPCs.
RPCs have various catalytic applications, e.g., direct/indirect
hydrogenation reactions, acceptor/acceptorless oxidative dehydro-
genation reactions, amination of alcohols, hydrolysis of amines,
hydroboration of terminal alkynes, cyclopropanation of olefins,
water splitting, alkynylation of carbonyl compounds with terminal
alkynes, transesterification, olefin metathesis, and alcohol racem-
ization. In addition, electronic and steric effects are two main
factors that have significant influences on the catalytic activities
of these superior types of pincer complexes during hydrogena-
tion and dehydrogenation reactions, due to: (i) the hemilability
and non-innocent behavior the pincer ligand, and (ii) the flexibil-
ity of the pincer framework (aliphatic versus aromatic). The pincer
149
ligands used by these RPCs could be tested with other earth-
abundant metals such as iron, copper, nickel, and cobalt. Given
the ease of pincer complex immobilization and the strong bind-
ing of pincer ligands to a metal center, heterogenization of RPCs
may prove to be particularly valuable in the development of tan-
dem systems. In these heterogeneous systems, metal leaching is
not likely to be a problem, which is promising for the development
of ruthenium pincer catalysts in industrial applications and other
pincer complexes.
Acknowledgments
The authors would like to express their deep appreciation of
the State Key Lab of Advanced Technology for Materials Synthesis
and Processing for financial support (Wuhan University of Tech-
nology). F.V. acknowledges the Chinese Central Government for an
“Expert of the State” position in the program of “Thousand talents,”
as well as the support of the Natural Science Foundation of China
(No. 21172027) and the Research Fund - Flanders (FWO) (project
No. 3G022912). H.A.Y. and N. A. express their deep appreciation of
the Chinese Scholarship Council (CSC) for financial support via their
PhD study grants 2012GXZ639 and 2012GXZ641, respectively.
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