Coordination Chemistry Reviews 344 (2017) 299–322

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Coordination Chemistry Reviews

journal homepage: www.elsevier.com/locate/ccr

Review

g5-Oxocyclohexadienyl ligands in transition metal chemistry: Neglected

(Brønsted) base ligands in cooperative catalysis
R
O

MLn

A. Igau
Laboratoire de Chimie de Coordination, CNRS 205 route de Narbonne, 31077 Toulouse, France
Université de Toulouse, UPS, INPT, 31077 Toulouse, France

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

Article history: This contribution gives an exhaustive view on the coordination chemistry of the largely neglected
Received 21 November 2016 internal p-bonded (Brønsted) base g5-oxocyclohexadienyl arene type ligands. Synthesis of
Accepted 1 March 2017 eta5-oxocyclohexadienyl transition metal complexes are easily achieved via a broad range of chemical
Available online 6 March 2017
pathways. Experimental analytical data recorded in the liquid and solid phase allowed to assign the
g5-geometry of the oxocyclohexadienyl ligand. From recent pioneering results, it is reasonable to antic-
Keywords: ipate that eta5-oxocyclohexadienyl transition metal complexes, ‘‘bifunctional Shvo-type species cata-
Phenolate
lysts”, are promising catalysts and deserve further experimental and computational studies with
Arene ligand
(Brønsted) base ligand
respect to structure/activity relationships. These species have a long way to go in coordination chemistry
Transition metal complexes extending their domain of applications.
Bifunctional catalysis Ó 2017 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
2. Oxocyclohexadienyl ruthenium complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
2.1. Sandwich oxocyclohexadienyl ruthenium complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
2.1.1. Synthesis from coordinatively saturated precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
2.1.2. Synthesis from coordinatively unsaturated precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
2.2. Half-sandwich oxocyclohexadienyl ruthenium complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
2.2.1. Synthesis from coordinatively saturated precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
2.2.2. Synthesis from coordinatively unsaturated precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304
3. Oxocyclohexadienyl non-ruthenium complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
3.1. Sandwich oxocyclohexadienyl non-ruthenium complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
3.1.1. Sandwich oxocyclohexadienyl manganese complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
3.1.2. Sandwich oxocyclohexadienyl iron complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
3.1.3. Sandwich oxocyclohexadienyl group 9 (Co, Rh, Ir) complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 307
3.2. Half-sandwich oxocyclohexadienyl non-ruthenium complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
3.2.1. Half-sandwich oxocyclohexadienyl group 6 (Cr, Mo) complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
3.2.2. Half-sandwich oxocyclohexadienyl manganese complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310

Abbreviations: dippe, 1,2-bis(diisopropylphosphino)ethane; TMANO, trimethylamine N-oxide; NMO, 4-methylmorpholine N-oxide; OTf, OSO2CF3; Cp*, C5Me5; Cp, C5H5;
Alk, alkyl; Ar, aryl; acac, acetylacetonate; cod, 1,5-cyclooctadiene; Cp, g5-C5H5; Cp*, g5-C5Me5; 9-BBN, 9-borabicyclo [3.3.1]nonane; LDA, lithium diisopropylamide, LiNiPr2;
DBU, 1,8-diazabicyclo[5.4.0] undec-7-ene; DME, 1,2-dimethoxy-ethane; bipy, 2,20 -bipyridine; phen, 1,10-phenanthroline; Nbipy, 4,40 -dinonyl-2,20 -bipyridine); dmpm,
1,2-bis(dimethylphosphino)methane; dppm, 1,2-bis(diphenylphosphino)methane; dppe, 1,2-bis(diphenylphosphino)ethane; dmpe, 1,2-bis(dimethylphosphino)ethane;
depe, 1,2-bis(diethylphosphino)ethane; dppp, 1,3-bis(diphenylphosphino)propane; dppb, 1,3-bis(diphenylphosphino)butane; dppf, 1,10 -bis(diphenylphosphino)ferrocene;
tol, toluene; coe, cyclooctene; tht, tetrahydrothiophene.
E-mail address: alain.igau@lcc-toulouse.fr

http://dx.doi.org/10.1016/j.ccr.2017.03.001
0010-8545/Ó 2017 Elsevier B.V. All rights reserved.
300 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322

3.2.3. Half-sandwich oxocyclohexadienyl osmium complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311

3.2.4. Half-sandwich oxocyclohexadienyl group 9 (Rh, Ir) complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
3.2.5. Half-sandwich oxocyclohexadienyl group 10 (Ni, Pd) complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312
4. Reactivity of oxocyclohexadienyl transition metal complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
4.1. Reactivity of oxocyclohexadienyl ruthenium complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
4.1.1. Reactivity of sandwich oxocyclohexadienyl ruthenium complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
4.1.2. Reactivity of half-sandwich oxocyclohexadienyl ruthenium complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 314
4.2. Reactivity of oxocyclohexadienyl non-ruthenium complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
4.2.1. Reactivity of sandwich oxocyclohexadienyl non-ruthenium complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
4.2.2. Reactivity of half-sandwich oxocyclohexadienyl non-ruthenium complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
5. Spectroscopic and X-ray analysis of oxocyclohexadienyl ligand in transition metal complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 316
5.1. Spectroscopic features of oxocyclohexadienyl ligand in transition metal complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 316
5.2. X-ray analysis of oxocyclohexadienyl type ligands in transition metal complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
6. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 320
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321

1. Introduction (CO)2] 3 and the remaining elusive 16-electron coordinatively

The heyday of organometallic chemistry started in the mid-20th
century. The interplay between the inorganic metal and the
organic ligands is of central importance in the chemistry of transi-
tion metal complexes for their catalytic [1], optoelectronic [2], or
medicinal [3] applications, to name but a few. The ligands directly
influence the performance of the metal complexes through their
electronic and steric effects.
The preparation of the ferrocene complex, Cp2Fe 1, in 1951 by
two independent research groups [4] and its correctly addressed
structure one year later by Wilkinson, Woodward et al. [5] as a
5-membered g5-cyclopentadienyl ring sandwich complex,
[(g5-C5H5)2Fe 1] (Chart 1), provided the starting point for the
extensive area of p-coordinated arene organometallic chemistry.
Other than sandwich complexes, half-sandwich (=piano stool)
cyclopentadienyl transition metal complexes I were also prepared
[6] (Chart 1).
A relevant example of the 5-membered cyclopentadienyl
ring in catalysis is the Shvo pre-catalyst 2 (Fig. 1). This dimeric
complex 2 thermally dissociates into two monoruthenium species,
the g5-cyclopentadienyl hydroxy compound [(g5-C5Ph4OH)Ru(H)
unsaturated complex 4 described as an g4-oxocyclopentadienyl
species 4b (‘‘keto-structure”) (Fig. 1) [7]. The Shvo dimeric pre-
catalyst 2 is one of the most versatile metal-ligand bifunctional
catalysts described so far; it efficiently promotes a number of envi-
ronmentally friendly and atom-economical chemical transforma-
tions with great functional group tolerance for a large scope of
substrates [8].
The pioneering studies on 5-membered p-coordinated
cyclopentadiene complexes revealed a new type of metal-carbon
bonding in which the metal orbitals interact with the p-electron
arene ligand. Since then, a multitude of p-systems incorporating
arene ligands with different transition metals were synthesized
and first tested as catalysts [9].
After the discovery of ferrocene, it was readily shown that,
in addition to the six electron p-system of the planar
g5-cyclopentadienyl ligand, 6-membered aromatic hydrocarbon
rings could act as g6-benzene type ligands for transition metals
[10]. In 1955, Fischer and Hafner obtained the prototype of these
compounds, (g6-C6H6)2Cr 5, isoelectronic with ferrocene (Chart 1).
Several synthetic routes have been developed for the preparation
of related bis(arene)metal complexes [11]. Sandwich and

R
O
Fe M Cr Ru Z Ru
X Z X Ph3 P H
Y Y Ph3 P

1 I 5 II 6

Chart 1. Prototypical examples of 5- and 6-membered sandwich, 1 and 5, and half-sandwich, I-II and 6 p-arene complexes.

Shvo active catalyst

Ph Ph Ph
Ph O O Ph
H Ph OH Ph O Ph O
Ph Ph Ph Ph Δ
Ph Ph
Ph Ru H Ru Ph Ru + Ph Ph Ph Ph 4
CO OC H Ru Ru
OC
CO OC CO OC OC
CO CO
2 3 4a 4b
Shvo dimeric pre-catalyst η5-hydroxy- η 5-cyclopentadienoxo η4-oxocyclopentadienyl
cyclopentadiene ( "oxanion-structure" ) ( "keto-structure" )

Fig. 1. Thermal decomposition of the Shvo dimeric pre-catalyst 2. Representation of the tautomeric g5-oxanion 4a and g4-keto 4b structures of the active monomeric
5-membered cyclopentadiene catalyst 4.
 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322 301

half-sandwich g6-arene metal complexes are also efficient 2. Oxocyclohexadienyl ruthenium complexes
catalysts or catalyst precursors for a wide range of reactions. In
view of their catalytic applications [12], the chemistry of 2.1. Sandwich oxocyclohexadienyl ruthenium complexes
half-sandwich ruthenium complexes containing 6-membered
g6-coordinated arene rings II has exponentially expanded 2.1.1. Synthesis from coordinatively saturated precursors
(Chart 1), representing nowadays one of the most versatile studied Phenol is an acidic alcohol having no geminal hydrogen atoms.
families of organometallic compounds [13]. By analogy with the The acidity of phenol is considerably enhanced on complexation to
5-membered ring g4-oxocyclopentadienyl complex 4b generated a transition metal. Thus, abstraction of its OH-hydrogen is a
from the thermal dissociation of the dimeric Shvo active pre- straightforward and easy way to synthesize g5-
catalyst I (Fig. 1), the first 6-membered p-aryloxide type complex, oxocyclohexadienyl transition metal complexes. Therefore, the
[LnM(p-OAr)], was published in 1976 by Cole-Hamilton, Young and g6-phenol salt [Ru(g6-C6H3Me3)(g6-C6H5OH)](BF4) 7 is readily
Wilkinson and structurally described as a g5-oxocyclohexadienyl deprotonated in the presence of base to give the corresponding
ruthenium compound [Ru(H)(g5-OC6H5)(PPh3)2] 6 (Chart 1) [14]. pale yellow crystalline g5-oxocyclohexadienyl salt [Ru(g6-
Aryloxide rings, ArO, exists as an equilibrium mixture of four C6H3Me3)(g5-C6H5O)](BF4) 8 (Scheme 1) [19].
resonance forms. When p-coordinated to a metal fragment In an identical manner, deprotonation of [Cp⁄Ru(g6-C6H5OH)]
[LnM], while the O-anionic form lead to a g6-phenoxide type ligand (OTf) 9 with Et3N yielded the neutral g5-oxocyclohexadienyl com-
A, complexation of the other mesomers referred to the plex [Cp⁄Ru(g5-C6H5O)] 10 (Scheme 2) [20].
g5-oxocyclohexadienyl ligand B (Fig. 2). When an aqueous solution of 2-cyclohexene-1-one in excess
Even though p-coordinated 6-membered ring aryloxide com- and [Ru(H2O)6](OTs)2 11 are heated for 24 h at 70 °C, complete
plexes, [LnM(p-OAr)], have been known for 40 years, to date, these aromatization of cyclohexenone takes place to form the bis-
complexes have been largely neglected. Little of their chemistry phenol cation complex [Ru(g6-C6H5OH)2](OTs)2 12. Deprotonation
has been reported and they have been totally ignored from of the bis-phenol cation complex [Ru(g6-C6H5OH)2](OTs)2 12 to
potential applications in a number of domains such as in catalysis the parent neutral sandwich bis- g5-oxocyclopentadienyl complex
and in medicinal chemistry. To our knowledge, these 6-membered [Ru(g5-OC6H5)2] 13 can be effected with KOH in water (Scheme 3)
ring species, analytically and structurally identified as and is indicated by a high field shift of the aromatic protons in the
g5-oxocyclohexadienyl transition metal complexes, 1
H NMR spectrum [21].
[LnM(g5-OAr)], have never been reviewed. This communication The chemospecific coordination of the [(p-cymene)Ru] metal
has the ambition to be a comprehensive review on fragment of the tyrosine aromatic side in the sandwich complex
g5-oxocyclohexadienyl transition metal complexes. 14 induced a marked enhancement in the acidity of the
Ruthenium complexes held a prominent position in the early p-hydroxy function. It exhibits the properties of a strong acid and
development of organometallic chemistry, and they continue to is effectively deprotonated in aqueous solution to give the
attract attention owing to the ability of such species to mediate corresponding g5-oxocyclohexadienyl ruthenium complex 15
myriad catalytic substrate transformations, often in a manner that (Scheme 4) [22]. Note that the same behavior was observed with
cannot be achieved by other metal complexes [15]. With the emer- dipeptides.
gence of bio-inorganic chemistry, the biological activity of p-arene
ruthenium complexes was explored [16]. Lately, p-arene metal
complexes have become popular building blocks for the prepara-
2
tion of metalla-assemblies [17]. It is therefore not so surprising OH O
i
to notice that ruthenium complexes are largely represented in Pr 2EtN
the family of transition metal with g5-oxocyclohexadienyl ligands. Ru
BF4
Ru
BF4
As a result, some sections of this review are subdivided into two 2 - iPr2 EtNH BF4
categories; ruthenium and non-ruthenium p-oxocyclohexadienyl
7 8
complexes.
The intent of this communication is to provide (i) the exhaus- Scheme 1. Synthesis of sandwich g5-oxocyclohexadienyl mesitylene ruthenium
tive synthetic pathways and reactivity of g5-oxocyclohexadienyl complex 8 [19].
transition metal complexes, (ii) a description of the most signifi-
cant analytical data of these p-arene-like complexes, and (iii) some
of the main prevalent activities of g5-oxocyclohexadienyl transi-
tion metal complexes observed so far in coordination chemistry OH O
[18]. The literature published up to September 2016 is covered. Et3N
Ru OTf Ru
Cp* - Et3NH OTf Cp*
9 10

O Scheme 2. Synthesis of sandwich parent g5-oxocyclohexadienyl ruthenium com-

plex 10 [20].

O O O
2
O OH O
A B KOH
6
η -phenoxide 5
η -oxocyclohexadienyl [Ru(H 2O) 6 ](OTs)2 Ru Ru
( "oxanion-structure" ) ( "keto-structure" ) O 24h, 70°c OH O
11
12 13
Fig. 2. Mesomeric forms of 6-membered ring aryloxide type ligands, ArO:
potential ambivalent g6-A and g5-B coordination mode in transition metal Scheme 3. Synthesis of sandwich bis(g5-oxocyclohexadienyl) ruthenium complex
chemistry. 13 [21].
302 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322

HOOC 3 HOOC 2 fragment is coordinated to 12-electron organometallic fragments

H CH 2 OH H CH 2 O as [Cp⁄Ru]+, have been synthesized and used for their relative bind-
H 3N Ru H 3N Ru ing affinities torward the estradiol receptor site. The existence of
H2 O radioisotopic ruthenium nuclei which are c-ray emitters may
extend these organometallic-labeled estrogens to the areas
14 15
of nuclear medicine. Investigations of the complexation of the
Scheme 4. Stabilisation of the g -oxocyclopentadienyl form of the aromatic side
5 [Cp⁄Ru] fragment, prepared from the addition of KPF6 on the
chain of the tyrosine in 15 [22]. [Cp⁄RuCl]2 precursor 19, at the 6-membered ring of b-estradiol
led to the mixture of the two g5-oxocyclohexadienyl
diastereoisomers a,b-[Cp⁄Ru(g5-estradienonyl)] 20a,b and the
R R a-[Cp⁄Ru(g6-estradiol)]+ 21. These complexes have been separated
R' O and fully characterized. Note that the authors demonstrate that the
R' NO2 KOH
(excess) reaction conditions and the counteranions have a determinant
BF 4
Ru Ru influence in the formation of the g5-oxocyclohexadienyl form of
Cp MeOH Cp the A-ring of the estrogen derivative 20a,b [24,25] (see Scheme 6).
16 a, R=R'=H 17a -c Reaction in pentane of the coordinatively unsaturated dimers
b, R=H, R'=Me [Cp0 Ru(OMe)]2 22a,b with phenol in excess proceeds slowly at
c, R=Me, R'=H ambient temperature to form the neutral g5-oxocyclohexadienyl
complexes [Cp0 Ru(g5-C6H5O)] 10 and 17a as bis(phenol) adduct
KOMe KOH
(1 eq) hydrogen-bonded to the oxygen atom of the six membered ring
10(HOPh)2 and 10(HOPh)2. This reaction requires 3 mol. of phenol
R per mol. of ruthenium to go to completion. Less phenol yields the
R' OMe same product but leaves unreacted [Cp0 Ru(OMe)]2 22a,b [20,26].
BF 4 The neutral g5-oxocyclohexadienyl complex [Cp⁄Ru(g5-C6H5O)]
Ru
Cp 10 was isolated as a white crystalline compound and was charac-
terized by X-ray diffraction analysis [20,27]. In addition to phenol,
18a -c substituted phenols, i.e., 5-isopropyl-2-methylphenol (carvacrol),
Scheme 5. Synthesis of g5-oxocyclohexadienyl ruthenium complexes 17a-c via
2,4-di-tert-butylphenol, o-hydroxy-acetophenone, and salicylalde-
C–O and C–N scissions [23]. hyde were investigated. Because of the constraint phenol ring, the
r- to p-rearrangement could last 2 weeks in benzene solution. The
polarity of the solvent plays an important role in the reaction
In a totally different approach, Kimura and co-workers reported course of phenol derivatives and coordinatively unsaturated
the quantitative conversion of sandwich electron deficient ruthenium precursors. r-Complexes show increased stability in
g6-nitroarene complexes [CpRu(g6-3,4-R,R0 C6H3NO2)](BF4) 16a-c less polar solvents. Koelle and co-workers investigated the reaction
to pure [CpRu(g5-3,4-R,R0 C6H3O)] 17a-c in the presence of excess between [Cp⁄Ru(OMe)]2 22b and phenols in benzene-d6 by
KOH in MeOH (Scheme 5) [23]. It was also demonstrated that, means of NMR spectroscopy. The authors succeeded to detect
starting with the same g6-nitroarene complexes 16a-c, addition r-intermediates in the formation of the corresponding
of 1 eq of KOMe led to the corresponding anisole g6-arene type g5-oxocyclohexadienyl complexes [28].
complexes 21a-c. Then, C–O bond scission of the methoxy arene Complex [Cp⁄Ru(g5-C6H5O)] 10 can also be prepared in better
bond in 18a-c occurs at room temperature with KOH by a yield from the metathesis reaction of the coordinatively
nucleophilic aromatic substitution mechanism to give after releas- unsaturated dimer [Cp⁄RuCl]4 23 and the thallium salt of phenol
ing MeOH the corresponding g5-oxocyclohexadienyl complexes (Scheme 8) [29]. Tilley et al. reported the reaction of bulky
17a-c (Scheme 5) [23]. lithium 2,6-di-tert-butylphenoxide with the same precursor 23
leading to the g5-phenolate adduct [Cp⁄Ru(g5-2,6-tBu2C6H3O)]
2.1.2. Synthesis from coordinatively unsaturated precursors 24a (Scheme 8). Yellow crystals are readily obtained by slow
Coordinatively unsaturated ruthenium precursors are prone to cooling of concentrated pentane solutions and the
give sandwich g5-oxocyclohexadienyl complexes. Several g5-oxocyclohexadienyl complex 24a was characterized spectro-
bioorganometallic compounds, in which the A-ring of b-estradiol scopically and by X-ray crystallography [30]. An analogous

1/ KPF6
Me OH
2/

O
RuCp* HO
HO + RuCp*
α-20a
(β-estradiol) α-21
[Cp*RuCl]2 +
19 THF Cp*Ru

O
β-20b

Scheme 6. Synthesis of g5-estradione ruthenium complexes 20a,b [24,25].

 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322 303

HOPh O
O PhOH
PhOH HOPh Ru
[Cp'Ru(OMe)] 2 Ru E 110 °C, 3h
- MeOH Cp' PhOH
22a,b -2 dmfm
17a (HOPh) 2 E
Cp'= Cp (a), Cp* (b) Ru E 29
10 (HOPh) 2
E E
E
Scheme 7. Synthesis of g5-oxocyclohexadienyl ruthenium complexes 10 and 17a-c O
as bis(phenol) adducts [26,27]. 28 PhOH E
Ru
130 °C, 3h E
O -2 dmfm
PhOTl 30
Ru
- TlCl Cp* Scheme 10. Synthesis of g5-oxocyclohexadienyl complexes 29 and 30 and ring-
10 closing transformation in the presence of dimethyl fumarate (dmfm, E = CO2Me)
tBu
1/4 [Cp*RuCl]4 and phenol [36].
tBu
23 R' OLi
R' O
R R plex, [Ru(g4-cod)(g6-cot)] gave the same results as 28 but in lower
Ru yields. Since complex 30 was considered to be generated from [Ru
Cp*
- LiCl (g6-cot)(dmfm)2] 28 via 29, transformation of complex 29 to 30
24 a, R= t Bu, R'= H
was investigated. Actually, when complex 29 was treated with
b, R= H, R'= t Bu
phenol in the presence of dmfm at 130 °C for 3 h, complex 30
Scheme 8. Synthesis of g5-oxocyclohexadienyl complexes 10 and its alkyl substi- was obtained in an NMR yield of 84% (Scheme 10) [36].
tuted congeners 24a,b [26,27].

2.2. Half-sandwich oxocyclohexadienyl ruthenium complexes

reaction was conducted with lithium 2,4-di-tert-butylphenoxide
and led to the corresponding g5-oxocyclohexadienyl complex
24b (Scheme 8) [28].
Perfluoro g5-oxocyclohexadienyl ruthenium complexes were
obtained via different ways. The yield of g5-oxocyclohexadienyl
complex [CpRu(g5-C6F5O)] 26a was optimum by the reaction of
[CpRu(g4-butadiene)Cl] 25 with the thallium(I) salt of pentafluo-
rophenol in refluxing THF (Scheme 9) [31]. Reaction of [Cp⁄Ru
(MeCN)3]Cl 27 with C6F5OTl in acetonitrile affords the correspond-
ing fluorinated analogue [Cp⁄Ru(g5-C6F5O)] 26b (Scheme 9) [32].
Similar reactions were conducted to obtain the corresponding par-
tially fluorinated complexes [RuCp⁄(g5-C5F5nHnCO)] (n = 1–4).
Note that depending upon the number and location of the fluorine
substituents, the complexes were isolated as adducts with one-half
of a molecule, one molecule, or no molecule of water [33].
The complex [Cp⁄Ru(g5-C6F5O)] 26b can also be prepared from
the addition of pentafluorophenol and the coordinatively unsatu-
rated dimer [Cp⁄Ru(OMe)]2 22b (Scheme 9) [34].
Ruthenium(II) g5-oxocyclohexadienyl complexes, 29 and 30,
were synthesized by simple and selective oxidative transformation
of [Ru(g6-cot)(dmfm)2] 28 (cot = 1,3,5-cyclooctatriene, dmfm =
dimethyl fumarate) with phenol (Scheme 10) [35]. The mechanism
of the ring contraction of cyclododeca-1,5,9-triene was not eluci-
dated. Without dmfm, the yield of 30 was drastically decreased.
The use of solvents such as toluene, THF, and 1,2-dichloroethane
with phenol in the absence of dmfm completely suppressed the
reaction, the starting complex 28 was almost recovered. Note that,
in the same reaction conditions, the zerovalent ruthenium com-
2.2.1. Synthesis from coordinatively saturated precursors
The first reported g5-oxocyclohexadienyl transition metal com-
plexes have been prepared and fully characterized by Wilkinson,
Cole-Hamilton and Young in 1976 [14]. When the coordinatively
and electronically saturated dihydrido precursor [Ru(H)2(PPh3)4]
31 is treated with phenol, g5-oxocyclohexadienyl hydrido complex
[(g5-OC6H5)Ru(H)(PPh3)2] 6 is quantitavely formed after evolution
of dihydrogen and released of two equivalents of PPh3 (Scheme 11).
Depending upon the reaction conditions and the recrystallisation
procedure, different g5-C6H5O-adducts, 6(PhOH)2, 6(MeOH), and
6(PhOH)(C6H5Me)0.5, may be isolated. In addition to phenol, pyro-
catechol and resorcinol were investigated and the corresponding
g5-oxocyclohexadienyl hydrido complexes were isolated as yellow
crystalline products [Ru(H)(g5-OC6H4OH)(PPh3)2{(OH)2C6H4}n] 33
(n = 2) and 34 (n = 0) respectively [36]. The same reactions
conducted with a structural identical dihydrido precursor [Ru
(H)2(PR3)4], but incorporating the non labile PMe3 phosphine
ligands, [Ru(H)2(PMe3)4] 32, led after addition of phenol to the ini-
tial formation of the ionic complex 35 which released dihydrogen
to give the O-bonded phenolate complex 36 (Scheme 11) [37].
The coordinatively and electronically saturated bis(dihydrogen)
hydrido precursor [Ru(H)2(H2)2(PCy3)2] 37 incorporating a bulky
and basic phosphine ligand was reacted with phenol to test
whether this reaction would lead to p- or r-bonded aryloxide
ligand. The reaction between phenol and 37 suspended in acetone
is slow at room temperature and leads after 20 h to a yellow
analytically pure precipitate of g5-oxocyclohexadienyl hydrido

F F C 6 F5OTl
F O [Cp*Ru(MeCN) 3 ]Cl
C 6F 5OTl F F 27
[CpRu(η4-butadiene)]Cl Ru
Cp' C 6 F5OH
25
1/2 [Cp*Ru(OMe)] 2
26a ,b
22b
Cp'= Cp (a ), Cp* ( b)

Scheme 9. Synthesis of perfluoro g5-oxocyclohexadienyl ruthenium complexes 26a,b [31–34].

304 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322

O
R= Ph
Ru
- 2 PPh3 Ph 3P H
- H2 PPh3
PR 3
PhOH 6
R 3P H
Ru
R 3P H PMe3 PMe 3
PR3 Me3 P H Me3 P H
R= Me OPh
31 R= Ph Ru H Ru
32 R= Me - 40 °C Me 3P
H 25 °C Me 3P OPh
PMe 3 - H2 PMe3
35 36

Scheme 11. Preparation of g5-oxocyclohexadienyl hydrido complex 6 [38].

two cis-tricyclohexylphosphines, PCy3, despite their large cone

O
OH angle. Interestingly, the bis(dihydrogen) hydrido precursor 37
Cy3 P
Ru
H reacts with excess of cyclohexanone at 80 °C for 20 h to give the
Cy3 P
H
- 3 H2 Cy 3P cyclometalated cyclohexyl g5-oxocyclohexadienyl complex 39
H H 38 after the loss of 5 equiv. of dihydrogen (Scheme 12). The reaction
Ru of 37 with cyclohexanone leads concomitantly to the dehydro-
H H
H genation of the cyclic ketone into a phenoxide ring and to the
Cy3 P
O activation of a cyclohexyl ring [38].
O
37 The results reported in this paragraph indicated that phenol
Ru
- 5 H2 Cy3 P derivatives contain an acidic proton which could protonate
Cy2 P hydrido metal precursors to form the r-aryloxy compound. If
39 labile ligands can decoordinate from the coordination sphere of
the transition metal precursor, then, after the r–p aryloxy
Scheme 12. Synthesis of half-sandwich g5-oxocyclohexadienyl cyclohexylphos- rearrangement, formation of the corresponding g5-
phine complexes 38 and 39 [38]. oxocyclohexadienyl complex may be observed. This strategy has
been exemplified starting with coordinatively unsaturated
precursors.
O

Ru 2.2.2. Synthesis from coordinatively unsaturated precursors

SiMe OH MeSi PCy 2 Four-coordinate 14-electron [(Cy-PSiP)RuX] (Cy-PSiP =
Cy2 P
Ru X PCy2 [j3-(2-Cy2PC6H4)2SiMe]) complexes 40a,b that adopt a highly
Cy2 P C6 H6 unusual trigonal pyramidal coordinationn geometry reacted
- HX quantitatively with 1 equiv of phenol to form the new
18-electron g5-oxocyclohexadienyl complex (Cy-PSiP)Ru(g5-C6H5O)
40a X= Ot Bu 41
41 (Scheme 13) [39].
40b X= N(SiMe3)2 The reaction of phenol with the cyclometalated carbene IMes
ligand of [RuH(IMesH)(PPh3)2] 42 in benzene resulted in the
Scheme 13. Synthesis of an g5-oxocyclohexadienyl complex 41 with a strong
r-donating silyl group [39].
g5-bonded phenolate moiety and loss of phosphine to form 45 as
an air-sensitive yellow solid complex (Scheme 14). There is no
reaction when the solvent is changed to THF. It was proposed that
complex [RuH(g5-C6H5O)(PCy3)2] 38 (Scheme 12). Product 38 is THF may coordinate to the vacant coordination site which prevents
analogous to its PPh3 congener 6; the g5-oxocyclohexadienyl phenol from coordinating and reacting. The reaction in benzene
hydrido ruthenium fragment [RuH(g5-C6H5O)] can accomodate may proceed via an O-bonded phenol intermediate 43 in which

Ph O
Ph H
N H PPh O O
N H PPh 3
3 PhOH Ru PhOH
Ru N Ru N Ru
N PPh3 PPh 3 PPh3
N PPh3 C D
6 6 O - PPh3 H H
H Ph N N

42 43 44 45

Scheme 14. Synthesis of g5-oxocyclohexadienyl carbene ruthenium complex 45 [40].

 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322 305

H R O
NaOC 6H 4 R OC 6 H 4R
Ph3 P Ru
RuH(Cl)(PPh 3 )3 Ru H
- NaCl Ph 3P
Ph3 P PPh 3 - PPh3
46 PPh3
47a,b 6 R= H
48b R= tBu

F F
H F O
NaOC 6F 5 Ph3 P OC 6 F5 F F
Ru Ru
H
- NaCl Ph3 P PPh 3 Ph3 P
- PPh3 PPh3
49 50

Scheme 15. Synthesis of g5-oxocyclohexadienyl complexes 6 and 48ab with sodium phenoxides [41].

Ph2 P
ONa
RuH(Cl)(PPh 3) 3 O PPh3
- NaCl, - 2 PPh 3 Ph2P Ru
46
H Me
51
Scheme 16. Synthesis of p-bound binaphthoxy complex 51 [41].
the phenol becomes acidic due to complexation. This acid can then
break the cyclometalated bond between IMes and ruthenium to
give 44 which initiates, in the presence of a second equivalent of
phenol, the r ? p isomerization of the phenoxide ligand to give
the final product 45 [40].
These studies demonstrates that cordinatively unsaturated
complexes can be easily protonated with phenol derivatives to
led to the formation of the corresponding g5-oxocyclohexadienyl
complexes.
Synthesis of g5-oxocyclohexadienyl complexes from coordina-
tively unsaturated precursors has also been achieved with arylox-
ide salts
In a pioneering study, sodium phenoxides NaOC6H4R (R = H (a),
t
Bu (b)) were reacted on the coordinatively unsaturated mono
hydrido precursor [Ru(H)(Cl)(PPh3)3] 46. Formation of the
corresponding g5-oxocyclohexadienyl complexes 48ab through
the O-bonded aryloxide intermediates 47ab were observed
(Scheme 15) [41]. The electron deficiency of the perfluorophenox-
ide ring NaOC6F5 inhibits the r ? p isomerization of the phenoxy
ring. In that case, formation of the corresponding p-bonded
g5-phenolate ring complex 50 was not observed, only the pentava-
lent complex 49 was isolated (Scheme 15). Using electron-deficient
perfluororophenolate ligands, both the basicity of the oxygen and
the p-donor capabilities of the ring are sharply attenuated.
Subsequent reaction in CH2Cl2 of 46 with racemic HO-MOP
(20 -(diphenylphosphino)-1,10 -binaphthyl-2-ol), converted into its
sodium salt by reaction with Na2CO3, gave after isolation, the
orange ‘‘tethered” binaphthyl [Ru(H)(O-MOP)(PPh3)] 51 complex
within a piano-stool structure (Scheme 16) [41]. Only one
diastereomer was formed during the chemical transformation.
The possibility of rapid epimerization of the metal center, given
the non-lability of the phosphine ligand in reactions with donors
such as carbon monoxide and acetonitrile; was excluded. The
binaphthol-derived O-MOP ligand in 51 is r-bounded through
phosphorus and in a p-bounded via the aryloxide ring. In the
absence of X-ray crystal structure and on the sole basis of NMR
O
PhOTl
i Ru
- TlCl Pr 3P H
PiPr 3
53
[RuH(Cl)(Pi Pr3 )2 ]2
Me
OLi
52 O
i Ru
Pr 3P H
- LiCl PiPr 3
54
Scheme 17. Synthesis of g5-oxocyclohexadienyl hydrido complexes 53 and 54
[42,43].
data, the authors were not able to unequivocally establish the hap-
ticity of the p-bound aryloxy ring in the binaphthyl framework in
51. Nevertheless, the authors proposed that the chemical shift of
the C–O aryloxy carbon atom at 155.6 ppm suggests a j1: g6 struc-
ture for 51.
The straightforward synthesis of the g5-oxocyclohexadienyl
hydrido complex 53 was performed by addition of thallium phe-
noxide TlOPh on the coordinatively unsaturated complex [Ru(H)
(Cl)(PiPr3)2]2 52 (Scheme 17) [42]. Reaction, with the same precur-
sor 52, of the monolithium salt of ortho-phenol proceeds to com-
pletion within 14 h at 20 °C in benzene, and the only observed
product is the corresponding g5-oxocyclohexadienyl complex 54
(Scheme 17) [43].
Fogg and co-workers demonstrated that phenoxide ions
KOC6H4R (R = H (a), tBu (b)) reacted in a straightful way on the
halogenated coordinatively unsaturated precursor [Ru(Cl)2(PPh3)3]
55, in non-alcohol solvents, to afford the g5-oxocyclohexadienyl
cyclometallated complexes [Ru(g5-OC6H4R)(o-C6H4PPh2)(PPh3)]
58a,b. It was proposed that 57a,b were generated via initially-
formed bis-phenolate pentavalent intermediate 56a,b (Scheme 18).
The availability of three coordination sites, arising from the coordi-
native unsaturation of 56a,b in conjunction with the lability of
bound PPh3, induces r ? p isomerization of one O-bonded pheno-
late ligand, OC6H4R, to give mixed r/p-aryloxide intermediate 57a,
b. The basicity of the phenolate oxygen within 57a,b leads to the
abstraction of an ortho-proton from the phenyl group of a remain-
ing PPh3 ligand, resulting in ortho-metallation, elimination of
phenol, and formation of solvated complex 58a,b (Scheme 18)
[44]. Note that in 20% MeOH/CH2Cl2, reaction of [Ru(Cl)2(PPh3)3]
55 with 2 KOC6H4R affords a mixture of g5-oxocyclohexadienyl
complexes 58a,b and [RuH2(CO)(PPh3)3] 59.
306 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322

R O
R O H
OC 6H 4R R O
2 KOC 6 H 4R
Ph3 P OC 6H 4R Ru
Ru(Cl) 2(PPh 3) 3 Ru Ph3 P OC 6 H 4R Ru
Ph 3P
- 2 KCl Ph3 P PPh 3 - PPh3 Ph2P H
55 Ph2 P
56a,b
R= H (a), t Bu (b) 58a,b
57a,b

Scheme 18. Synthesis of g5-oxocyclohexadienyl chelate ruthenium complexes 58a,b [44].

R2 N R 2N
R 2N CsF, PR'3 O O
N Ru N N
Ru Ru
P Cl - CsCl, - [Si]F P PR'3 P
Ph2 Cl - p-cymene Ph 2 Cl Ph2 Cl
60 61 63
[Si]O
R 2N
CsF O PR' 3
N Ru
- CsCl, - [Si]F
P
- p-cymene Ph 2 Cl
2
62

Scheme 19. Synthesis of tethered g5-oxocyclohexadienyl complexes 61 and 62 (R = iPr, [Si] = SiMe2tBu) [45].

In the area of p-coordinated arene organometallic chemistry, Me

particular attention has been devoted to the development of
Me
arene-tethered complexes in an attempt to improve the stability 3 OH Ar
O O
of these species and to increase stereocontrol at the metal center Me
n= 3
of chiral catalysts [12,13]. Mn Me + CpMn MnCp
Half-sandwich tethered g5-oxocyclohexadienyl Ru(II) com- - 3 CpH Cp O
plexes 61 have been recently prepared in a one pot procedure after Ar
65
successive addition of cesium fluoride salt and phosphines PR0 3 66
n Cp2 Mn t
(R0 = alkyl, aryl, alkoxy, aryloxy, amino group), on the p-cymene Bu
N-phosphino amidine precursor 60 [45]. After addition of CsF on 64 t
Bu
OH Ar
60, an air stable g5-oxocyclohexadienyl half-sandwich dimer O O
ruthenium(II) complex 62 was isolated and fully characterized tBu t
CpMn MnCp Mn Bu
(Scheme 19). The bimetallic product 62 is the precursor of the cor- n= 1 - CpH O Cp
responding 16-electron mono-metallic species 63, isoelectronic to Ar
68
the active species 4 formed after the thermal dissociation of the
67
bimetallic Shvo catalyst 2 (Fig 1).
Scheme 20. Synthesis of paramagnetic g5-oxocyclohexadienyl manganese com-
3. Oxocyclohexadienyl non-ruthenium complexes plexes 65 and 68 [46].

3.1. Sandwich oxocyclohexadienyl non-ruthenium complexes

3.1.1. Sandwich oxocyclohexadienyl manganese complexes
Coordination chemistry of phenoxide ligands to Mn(II) was
investigated because of the possible implication of Mn(II)–phenox-
ide complexes as intermediates in the phenylphosphate carboxy-
lase enzyme, a protein which catalyses the selective
carboxylation of phenylphosphate to 4-OH-benzoic acid
using CO2. The synthesis and characterization of 2,6-substituted
g5-oxocyclohexadienyl complexes 65 and 68 were then reported.
Bulky substituents in both 2- and 6-position of the phenyl ring,
as well as an unsaturated coordination of the metal, force
p-phenoxy bonding to the metal center. When [Cp2Mn] is reacted
in anhydrous THF with 2,6-tBu2C6H3OH in a 1:1 molar ratio a white
solid product is observed. The initial formation of a high spin spe-
cies, most probably the O-bonded phenoxide complex 67, the
kinetic product, converts in a short time into a low spin species.
The complex bearing the phenoxy moiety p-bonded to the metal
68 is the thermodynamic product [46]. These complexes 65 and
68 were the first examples of phenoxide p-coordination to a para-
magnetic center (see Scheme 20).
3.1.2. Sandwich oxocyclohexadienyl iron complexes
Neutral g5-oxocyclohexadienyl iron complex 70 is readily pre-
pared from the chlorobenzene complex 69 by reaction with excess
KOH in 50% aqueous acetone (Scheme 21) [47].
Heterolytic C–O cleavage of aryl ethers is activated by the
[Cp0 Fe]+ fragment in 71a-c whose driving force is the formation
of the g5-oxocyclohexadienyl complexes 70 and 72. This cleavage
reaction is effected by KOH (or tBuOK) at room temperature
(Scheme 22) [48]. These mild cleavage conditions strongly contrast
 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322 307

Me
Cl O Ar
Me O
KOH OK
Fe Fe O Li FeCp'
Cp H 2O/acetone Cp Me Me O
[Cp'FeBr] 2 Fe Ar
69 70 LiBr Cp'
75
Scheme 21. Synthesis of g5-oxocyclohexadienyl iron complex 70 from chloroben- Cp' = C5HiPr4 78
zene complex 69 [47].
Scheme 25. Synthesis of paramagnetic g5-oxocyclohexadienyl iron complex with
lithium cation adduct 78 [51].

OR' O
KOH Several reactions of complex [Cp0 FeBr]2 75 with
Fe Fe 2,6-dimethylphenolate gave oily product mixtures that could not
Cp' DME Cp'
be characterized. Only when lithium bromide was added and the
71a-c 70 Cp'= Cp reaction mixture with 2,6-dimethylphenolate was worked up after
R'= Me (a), Ph (b), 72 Cp'= Cp* only 10 min of stirring at room temperature, could the paramag-
CH2CH2SiMe3 (c) netic g5-oxocyclohexadienyl complex 78 be obtained in low yield
by crystallisation (Scheme 25). The crystal structure of 78 reveals a
Scheme 22. Synthesis of g5-oxocyclohexadienyl iron complexes 70 and 72 via C–O
lithium cation coordinated to the oxygen donor sites of one
bond cleavage [49,49].
bis(l,j-O-2,6-dimethylphenolato)(tetraisopropylcyclopentadienyl)
ferrate(II) anion and to the oxocyclohexadienyl part of another iron
sandwich (Scheme 25) [51].
Depending on the substitution pattern of the phenols, the reac-
Me OEt O tion of [Cp0 Fe(N(SiMe3)2] 79 with substituted phenols led either to
tBuOK, CH 2CH=CH2Br j1-O phenolate or g5-p compounds. The reaction of 79 with
Fe Fe 2,6-tBu,4-R-phenols (R = H, Me) in solution is instantaneous, the
Cp THF Cp
transformation is accompanied by a color change from orange-
73 74 red to purple to give the diamagnetic g5-oxocyclohexadienyl
complexes 81a,b. The monomeric one-legged piano stool
Scheme 23. Synthesis of an g -oxocyclohexadienyl dendron iron complex 74 [50].
5

j1-O phenolate compounds 80a,b precede the formation of the

g5-oxocyclohexadienyl compounds 81a,b [52]. Note that a third
t
tBu
butyl substituent in the para position of the phenol compound
prevent formation of the p-coordination mode (see Scheme 26).
t
OK Bu
tBu
O 3.1.3. Sandwich oxocyclohexadienyl group 9 (Co, Rh, Ir) complexes
t
Bu Deprotonation of complex 82 was readily achieved by
Fe
Cp' treatment with sodium carbonate to give the corresponding
t
g5-oxocyclohexadienyl cobalt complex 83. Interestingly the simi-
Bu 76
[Cp'FeBr]2 lar complex 83 was prepared after alkylation of the duroquinone
t cobalt complex 84 (Scheme 27) [53].
Bu OK
75 tBu Reaction of anhydrous CoCl2 85 with 2 equiv of NaOAr
t
Bu (OAr = 2,6-di-tbutyl-4-methyl-phenoxide) in toluene at 80 °C over-
Cp'Fe O tBu
night led after work-up to the sandwich cobalt complex 86 bearing
Cp' = C 5H iPr 4
t
Bu two g5-oxocyclohexadienyl ligands in 26% yield. Based on their
77 previous results, the authors propose that the solvent has great
influence on the formation of the final product which might be a
Scheme 24. Synthesis of an 2,6-substituted g5-oxocyclohexadienyl iron complex reflection of radical behavior of the aryloxide ligand (Scheme 28)
76 [51]. [54].
As early as 1977, Maitlis and co-workers described the prepara-
with the drastic conditions required (200 °C, 10% yield) for the tion of the parent g5-oxocyclohexadienyl [Cp⁄M] rhodium 91 and
same reaction in the absence of the iron metal fragment. Note that iridium 92 complexes The solvated complexes [Cp⁄M(acetone)3]
an in situ generation of 70 was reported via the same heterolytic (PF6)2, 87 (M = Rh), and 88 (M = Ir) prepared in situ from [Cp⁄M
C–O cleavage of aryl ethers [49]. (Cl)2]2 and AgPF6 in acetone, reacted with phenol to give the
Reaction of [CpFe(g6-p-EtOC6H4Me)][PF6], 73, with tBuOK or hydrogen-bonded dimeric phenol complexes 89 (M = Rh), and 90
KOH and allyl bromide in THF gives both the triallylation of the (M = Ir) which were easily deprotonated with sodium carbonate
acidic methyl substituent and the heterolytic cleavage of the to the corresponding g5-oxocyclohexadienyl complexes 91
O-Me bond, which leads to the triallyl g5-oxocyclohexadienyl (M = Rh), and 92 (M = Ir) (Scheme 29) [55].
complex 74 (Scheme 23) [50]. Investigations of the complexation of the [Cp⁄Rh(acetone)3]2+
From the reaction of [Cp0 FeBr]2 75 with potassium 2,6-di(tert- fragment 87 at the phenolic ring of 17b-estradiol followed by
butyl)phenolate, the sandwich tetraisopropylcyclopentadienyl dia- treatment of NEt3 led to the formation of a mixture of 2 products
magnetic g5-oxocyclohexadienyl complex 76 was obtained in high a-[Cp⁄Rh(g5-estradienonyl)]2+ a-93, and b-[Cp⁄Rh(g5-
yield as red-purple moderately air-stable crystals. Note that a third estradienonyl)]2+ b-93. These complexes are separated and fully
alkyl substituent in the para position of the phenolate prevent the characterized. The X-ray structure of a-93, in which the
formation of the p-coordination mode; the corresponding organometallic moiety ‘‘Cp⁄Rh” is coordinated to the a-face of
r-phenolate complex 77 is formed (Scheme 24) [51]. the A-ring of the hormone was reported. In this compound the
308 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322

t
Bu

R OH tBu
tBu
t R O
Bu
t
[Cp'Fe(N(SiMe 3 )2 ] Cp'Fe O R Bu
Fe
79 - HN(SiMe3 )2 tBu Cp'

Cp' = 1,2,4-tBu3C5H2 80a - c 81a ,b

R= H (a), Me (b), tBu (c)

Scheme 26. Synthesis of diamagnetic g5-oxocyclohexadienyl iron complexes 81a,b [52].

2 2

MeO OH MeO O O O
Na2 CO3 MeI, AgPF6
Co Co Co
Cp* Cp* Cp*
82 83 84

Scheme 27. Synthesis of g5-oxocyclohexadienyl cobalt complex 83 [53].

t
3,5-dimethylphenol (b) and 3,4-dimethylphenol (c)) and subse-
Bu
quent treatment with NEt3. X-ray molecular structure of 96b con-
t
1.5 ONa Bu firmed the g5-structure geometry of the aryloxy ring (Scheme 32)
t
Bu
O [59]. Note that when the neutral iridium g4-diene complexes 97a,
b were exposed to HBF4 the corresponding g5-oxocyclohexadienyl
t
CoCl2 t Co Bu
Bu
85 - LiCl iridium complexes 92 and 96b were formed with liberation of
O
MeOH (Scheme 32) [59]. An identical reaction process was investi-
t
Bu
86
gate in the formation of g5-oxocyclohexadienyl crown-ether
iridium complexes [59].
Scheme 28. Synthesis of sandwich bis(g5-oxocyclohexadieny cobalt complex 86 Facile C–O bond scission of aryl ether Ar–OR bond (R = Me (a), Et
[54]. (b), Ph (c)) coordinated on electrophilic pentamethylcyclopentadi-
enyl iridium fragment [Cp⁄Ir] in sandwich arene complexes
98a-c occurs in buffered neutral water. Hydrolysis proceeds rapidly
at room temperature by a nucleophilic aromatic substitution
A-ring loses its planar character by adopting an g5-coordination mechanism to form the g5-cyclohexadienyl transient intermediate
mode. An identical reaction was conducted with the [Cp⁄Ir(ace- 99a-c which give after releasing alcohol ROH the corresponding
tone)3]2+ fragment 88 to form the corresponding iridium a- and g5-oxocyclohexadienyl complex 92 (Scheme 33) [60].
b-g5-estradienonyl complexes a-94 and b-94 [56]. The a- and In a similar approach, by increasing the electrophilicity of the
b-g6-estradiol complexes are quantitatively transformed in arene ring through g6-coordination on the pentamethylcyclopen-
coordinating basic solvents such as DMSO and MeCN, to the tadienyl iridium fragment [Cp⁄Ir], the aromatic C–H to C–O trans-
thermodynamically stable a- and b- g5-estradienonyl complexes formation of compound 100 proceeds through nucleophilic attack
a-93,94 and b-93,94 [57] (see Scheme 30). to form g5-cyclohexadienyl derivatives 101–105, and in the sec-
Treatment of [Cp⁄Rh(acetone)3][X]2 87 with 2-alkylphenols fol- ond step by oxidation with an appropriate oxidizing reagent to
lowed by O-deprotonation with NEt3 afforded the corresponding form the g5-oxocyclohexadienyl complex 92 [61]. Interestingly,
g5-oxocyclohexadienyl complexes 95a,b as microcrystalline C–O bond formation occurs at the position of least electron density
yellow solids in excellent yields (Scheme 31). X-ray structural data and selectively ortho to electron-withdrawing groups; only one
for 95b confirm the g5-coordination mode of the 6-membered isomeric product was observed. Different nucleophile/oxidant
arene-type ligand [58] (Scheme 31). combinations were tested to learn about the nucleophilic attack
In an analogous experimental conditions, but with the and oxidation steps that lead to C–O bond formation. Based on
iridium precursor [Cp⁄Ir(acetone)3](BF4)2 88, a series of the observed positional selectivity and the formation of
g5-oxocyclohexadienyl iridium complexes [Cp⁄Ir(g5-C6H2(R1)(R2) g5-cyclohexadienyl adducts with oxygen nucleophiles, the mecha-
(R3)O)](BF4) 92 and 96b,c were prepared in very good yields after nistic hypothesis for the C–O bond forming reaction involves
addition of the appropriate alkylated phenol (phenol (a), nucleophilic attack of chlorite NaClO2 on arene complex [Cp⁄Ir

3
O H O O
C 6 H5 OH Na2 CO3
[Cp*M(acetone) 3 ](X)2 M M (X )3 M X
Cp* Cp* H2 O Cp*
87 ,88 89 ,90 91 ,92
M=Rh 87, 89,91
X= PF 6
M=Ir 88, 90,92

Scheme 29. Synthesis of the parent g5-oxocyclohexadienyl [Cp*M] rhodium 91 and iridium 92 complexes [55].
 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322 309

Me OH

HO Cp*M
(17β-estradiol) , NEt 3
O
[Cp*M(acetone) 3 ](X) 2 + O
MCp*
87,88 α- 93,94 β-93 , 94
M= Rh, X= OTf, PF6, BF4 87 , 93
M= Ir, X= BF4 88 , 94

Scheme 30. Synthesis of the a- and b-g5-estradienonyl complexes a-93,94 and b-93,94 [56,57].

CHR2
2 OH
OH CHR2 OR O
OH OR
O
NEt 3 Ir Ir Ir + HOR
X Cp*
[Cp*Rh(acetone) 3 ](X)2 Rh Cp* Cp*
Cp* 98a-c 99a-c 92
87
R=H (a), Me (b ) 95a,b
Scheme 33. Synthesis of parent g5-oxocyclohexadienyl iridium complex 92 via
X=BF 4 C-O bond scission [60].

Scheme 31. Synthesis of sandwich 1-alkyl substituted g5-oxocyclohexadienyl

rhodium complexes 95a,b [58].
(g6-C6H6)] 100 followed by oxidation to generate the g5- oxocy-
clohexadienyl complex 108 and hypochlorous acid, possibly
through a syn elimination. In a reaction analogous to that with
NaClO2, complex 100 reacts with m-chloroperbenzoic acid
(mCPBA) in the presence of Na2CO3 to give 92 in 85% yield. Note
that the g5-cyclohexadienyl adduct of m-chloroperbenzoate 102
was observed by NMR spectroscopy. Evaluation of the combination
of hydrogen peroxide, a nucleophilic oxidant H2O2 and Na2CO3
resulted in a dialkylated peroxide g5-cyclohexadienyl adduct 103
which could be isolated and characterized. Monoalkylated perox-
ide adduct 103 could be observed by NMR and is likely on-path
in the formation of 104. Adduct 104 was observed to form complex
92 in low conversion (5%). The hypothesis is a syn elimination in
the cases of NaClO2 and mCPBA. Reaction of complex 100, H2O,
Na2CO3, and [4-NHAc-TEMPO](BF4), a reagent known for oxidation
of alcohols to aldehydes or ketones, results in isolation of the g5-
oxocyclohexadienyl complex 92 in 79% yield. Formation of adduct
105 is observed, and can be isolated if the reaction is run in the
absence of oxidant [61] (see Scheme 34).
By conceptually reversing the role of the arene in C–H function-
alization chemistry (from nucleophile to electrophile), p-arene
activation provides a new platform for the synthesis of arenes that
makes use of nucleophilic functionalization reagents and gives
products with complementary selectivity to traditional
approaches. Activation of the aromatic p-system has great poten-
tial as an alternative approach to C–H functionalization chemistry.
3.2. Half-sandwich oxocyclohexadienyl non-ruthenium complexes
3.2.1. Half-sandwich oxocyclohexadienyl group 6 (Cr, Mo) complexes
Trahanovsky and Hall reported an original route for the synthe-
sis of half-sandwich g5-oxocyclohexadienyl chromium complexes
[62]. Tethered g6-arene chromium complexes 106a,b were purged
with nitrogen and placed in the dark for 4 days; cleavage of the
C–O alkyl bond occurred to give the corresponding isomeric
g5-oxocyclohexadienyl allyl chromium complexes 107a,b as air-
stable, moderately water-soluble orange crystalline solid
(Scheme 35). Note that immediate formation of 107a,b was
observed after addition of boron trifluoride etherate on 106a,b to
give the corresponding g5-oxocyclohexadienyl BF3 O-adduct
108a,b. In the latter case, the mechanism for the reaction catalyzed
by the Lewis acid boron reagent involves initial complexation of
the BF3 followed by cleavage of the oxygen allyl bond [62].
More than a decade later, g5-oxocyclohexadienyl chromium
complexes 110a-c were conveniently prepared through their
corresponding phenol derivatives 109a,c with various bases (nBuLi,
Et4NOH) (Scheme 36) [63]. These g5-oxocyclohexadienyl chro-
mium complexes 110a-c were isolated as crystalline compounds

R1

R2 OH R1 R1 OMe
R3 R2 O R2 O
, NEt3 R3 X HBF4 R3
[Cp*Ir(acetone) 3](X) 2 Ir Ir
Cp* - MeOH Cp*
88 - HNEt3BF4
X= BF 4 92, 96b,c 97a,b
a R1,R2,R3= H
b R1= Me, R2= H, R3= Me
c R1= Me, R2= Me, R3= H

Scheme 32. Synthesis of g5-oxocyclohexadienyl iridium complexes 92 and 96b,c [59].

310 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322

O Cl
NaClO2 H O
Ir
Cp* - HOCl
101 85% (from 102)

O O
C6 H 4Cl
O OH O O
Cl
Na2 CO3 H 3h
Ir
Cp* - ClC6 H4 CO2H
2
H 102 85% (from 102) O

Ir Cp* Ir
Cp* Cp*
Ir
100 O OH H 92
H 2O 2 (aq),
H O O
Na2CO3 5d
Ir
Cp* H 5%
Ir (from 106)
103 Cp*
104

O H
AcHN N O
H2 O, Na2CO3 H
Ir
Cp* 79%
(from 102)
105

Scheme 34. Synthesis of g5-oxocyclohexadienyl iridium complex 92 via aromatic C–H to C–O conversion [61].

R R hypothesize that, in accordance with the high relative nucle-

O O ophilicity and potential reducing power of nBuLi, the tosylate
R 4d R derivative is cleaved into g5-oxocyclohexadienyl chromium 110a
Cr Cr and sulfenium anions (Scheme 36).
OC C 6 H6 OC
CO CO The diamagnetic g5-oxocyclohexadienyl molybdenum complex
114, resulting from ether demethylation was synthesized by oxida-
106a ,b 107a ,b
tion of 112 with 2 equiv. of silver trifluoromethanesulfonate
R= H (a), Me (b) (AgOTf) (Scheme 37) [64]. Upon treatment of 112 with AgOTf,
HN iPr2 the solution initially turned purple, consistent with the formation
R of the one-electron-oxidized product 113 and then became pale-
BF3 BF3
yellow-orange via further oxidation and loss of CO. Note that after
O
addition of Lewis acid B(C6F5)3 on compound 112 under exposure
R
Cr of O2, complex 113 was observed and led partially to the formation
OC
of 114 resulting also from ether demethylation (Scheme 37).
CO
Independent synthesis of 114 was also successfully achieved by
108a ,b addition of MeOTf to 115 (Scheme 37).

Scheme 35. Synthesis of g5-oxocyclohexadienyl chromium complexes 107a,b by

cleavage of C–O allyl bond [62].
3.2.2. Half-sandwich oxocyclohexadienyl manganese complexes
Pauson and co-workers, in 1981, reported the preparation of an
R R R g5-oxocyclohexadienyl manganese complex [(g5-C6H5O)Mn(CO)3]
R' OH R' O R' OTs 117a via the readily deprotonation reaction with bases of the cor-
2 nBuLi
Et4NOH responding g6-phenol precursor 116a (Scheme 38) obtained after
Cr R Cr R Cr R
OC CO H2 O, 20°C OC CO OC CO hydrolysis of [(g6-C6H5F)Mn(CO)3] [65]. g5-Oxocyclohexadienyl
CO - LiOTs
CO CO tricarbonylmanganese complexes 117b-d derived from ortho-,
109 a, R= R'= H 110a -c 111a meta-, and para-cresol have been prepared following an identical
b, R= Me, R'=H
experimental procedure [66]. It is only more than a decade later,
c, R= R'= Me
that single crystals of [(g5-C6H5O)Mn(CO)3] 117a suitable for
Scheme 36. Synthesis of half-sandwich g5-oxocyclohexadienyl chromium com- X-ray studies were grown in solution. In parallel, the preparation
plexes 110a-c [63]. of g5-oxocyclohexadienyl phosphine complexes via addition of
NMO or TMANO (1 equiv) oxidants and PR3 (3 equiv) to 116a led
with tetraethylammonium as countercation. The p-phenyl tosylate to air-stable orange solids complexes [(g5-C6H5O)Mn(CO)2PR3)]
chromium precursor 111a reacts with 2 equiv of nBuLi to form 118 (R’ = Ph) and 119 (R’ = OMe) in good yields and formation of
110a as the only isolable organometallic product. The authors 118 was confirmed by the X-ray study (Scheme 38) [67]. Note that
 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322 311

CO OC CO OC CO
CO
i i 2 AgOTf i i MeOTf i
Pr2 P Mo 0
P Pr 2 Pr 2P Mo II
P Pr2 Pr2 P Mo Pi Pr2
OC
- Me

MeO OMe MeO O O O

112 114 115

- CO
2 B(C 6 F5 )3
O 2 (1 atm)
CO 2-
CO BArF3
i I i
Pr2 P Mo P Pr 2 O
rt, CD2 Cl2
OC
O

MeO OMe BArF3

2
113

Scheme 37. Synthesis of half-sandwich tethered g5-oxocyclohexadienyl molybdenum complex 114 [64].

R R 5 h (Scheme 39). By deprotonation of the g6-phenol complex 122

with tBuOK, complex 121 was formed and appeared to be
O OH O
oxidant t
BuOK extremely unstable product at room temperature in solution. The
Mn Mn Mn oil 121(PhOH) generated from the deprotonation with NaOPh
OC PR'3 PR'3 OC CO OC CO can be handled without much difficulty and sequential addition
CO CO CO
of phenol allowed one to isolate 121(PhOH)5 in agreement with
118 R'= Ph (TMANO) 116a-d 117a-d
the formation of a solvation sphere with five phenol molecules
119 R'= OMe (NMO) a R= H, b R= o-Me, (Scheme 39) [69].
c R= m-Me,d R= p-Me

Scheme 38. Synthesis of half-sandwich g5-oxocyclohexadienyl manganese com-

plexes 117a-d, 118,119 [65–68].
Rauchfuss and coworkers mentioned the deprotonation reaction in
aqueous NaOH of the p-bonded guaiacol complex to give the
resulting g5-guaiacolate complex. Guaiacol features the hydroxyl
and methoxy groups characteristic of lignol monomers which are
derivatives obtained from biomass [68].
3.2.3. Half-sandwich oxocyclohexadienyl osmium complexes
It is only very recently that the g5-oxocyclohexadienyl half-
sandwich osmium complex 121(PhOH)5 was prepared as a brown
oil in 93% isolated yield by reaction of the hexahydride complex
120 with 6 equiv. of phenol in toluene heated under reflux for
3.2.4. Half-sandwich oxocyclohexadienyl group 9 (Rh, Ir) complexes
The material obtained by reaction of [(C2H4)2Rh(m-Cl)]2 123
with NaOPh consists in a mixture of two complexes, the dimer
Rh2(m-OPh)2(C2H4)4 125 in which the phenoxide acts as an
O-bonded ligand bridging the two Rh-atoms and the p-bonded
g5-oxocyclohexadienyl complex [(C2H4)2Rh(g5-OPh)] 124
(Scheme 40) [70]. The two pure compounds have been separated
after a long fractional crystallisation procedure. Despite several tri-
als, it was not possible to set up a selective procedure for one of the
two species 124 and 125.
The reaction of [(dppe)RhCl] 126 with NaOPh affords, after crys-
tallisation, a brown material containing chlorinated species and
the oxide of the dppe ligand and an orange solid that analyses cor-
rectly for the air sensitive g5-oxocyclohexadienyl complex 127
(Scheme 41) [70].

i H O (HOPh) 5 OH
Pr3 P
H 6 PhOH 1. NaOPh
H
Os Os Os
H H - 3 H2 i Pr P PiPr 3 i Pr P PiPr 3
i Pr P
3 2. 5 PhOH 3
3 H H H
120 121 (HOPh) 5 122

Scheme 39. Synthesis of g5-oxocyclohexadienyl hydrido osmium complexes 121(PhOH)5 [69].

O
+ 2 NaOPh
[(C 2H 4) 2Rh(μ-Cl)]2 Rh + [(C 2 H4 )2 Rh(μ-OPh) ]2
- 2 NaCl 125
123
124

Scheme 40. Synthesis of g5-oxocyclohexadienyl ethylene rhodium complex 124 [70].

312 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322

O methane from [(Ph3P)3Rh(m-Cl)]2 128 with 2 NaOAr [72] (see

NaOPh Scheme 43).
[(dppe)RhCl ] Rh + brown material Formation of the O-bonded phenoxy-hydride 141 from the bin-
- NaCl Ph 2P PPh2 uclear dihydride 139 comes with another product which grows in
126
the presence of excess phenol. This product has been identified as
127 the g5-oxocyclohexadienyl complex [(dippe)Rh(g5-C6H5O)
(HOPh)2], 140 with phenol units hydrogen-bonded to the carbonyl
Scheme 41. Synthesis of g5-oxocyclohexadienyl diphosphine chelate rhodium
function. Preparation of 140 can also be achieved by the addition of
complex 127 [70].
excess phenol to the (dippe)rhodium allyl derivative 142
(Scheme 44). lnterestingly, attempts to generate 140 without the
t
hydrogen-bonded phenol units by the direct addition of exactly
Bu one equivalent of phenol to the allyl complex 142 resulted in the
tBu
Me OLi isolation of the starting allyl 142 and 140 in a 2:1 ratio, respec-
Me O tively [73].
tBu t
[Rh(Cl)(PPh 3 )2 L] Rh Bu Preparation of g5-oxocyclohexadienyl rhodium complex 131
- LiCl, - PPh3 was achieved from the amido precursor 143 and the corresponding
128 L= PPh3 Ph 3P L
phenol derivative. Single crystal X-ray characterization confirm the
129 L= CO 131 L= PPh3 p-coordination of the aryloxy ligand (Scheme 45) [74].
132 L= CO In methanol, the tethered g6-aryloxy-alkylphosphine
tBu compounds 144a,b react with potassium hydroxide or potassium
t tert-butoxide in methanol to give g5-oxocyclohexadienyl iridium
Bu
Me OLi complexes 145a,b, which were isolated in moderate yield
Me O
tBu (Scheme 46). The species 145a,b have been fully characterized by
t
Bu elemental analysis, mass spectrometry, and multinuclear NMR
1/2 [L2Rh( μ-Cl)]2 Rh
- LiCl spectroscopy. The structure of the g5-oxocyclohexadienyl ligand
123 L2= (C2H4)2 L L has been further confirmed by an X-ray diffraction study on com-
130 L2= 1,5-C8H12 plex 145a. Formation of complexes 145a,b is a consequence of
133 L2= (C2H4)2 the presence of the methoxide ion which induces proton abstrac-
134 L2= 1,5-C8H12 tion on the carbon atom of the ligand side-chain, leading to the
breaking of the alkyl C–O bond and the concerted formation of
Scheme 42. Synthesis of 2,4,6-alkyl substituted g5-oxocyclohexadienyl rhodium
complexes 131–134 [71].
the new C–C bond. The final complexes require further
tautomerization of the probably formed g6-phenoxide ligand into
Addition of the phenoxide ion 2,6-tBu2-4-MeC6H2OLi on the g5-oxocyclohexadienyl ligand. Note that this process is further
chlororhodium precursors 123, 128–130 gave the corresponding complicated by the formation of phenol in the reaction media,
complexes [(2,6-tBu2-4-MeC6H2O)RhL2] (2 L = 2 PPh3 (131); CO, which most likely results from the protonation of the
PPh3 (132); 2 C2H4 (133); 1,5-C8H12 (134)) containing the g5-oxocyclohexadienyl ligand by the solvent and that is probably
phenoxide ion as an g5-bonded oxocyclohexadienyl ligand. These responsible for the moderate yield of the reactions. In fact, crystals
g5-oxocyclohexadienyl complexes 131–134 have been spectro- of complex 145a were obtained as the phenol solvate [75].
scopically characterized, as well as by X-ray structure determina-
tions of the CO/PPh3 132 and chelate 134 half-sandwich
derivatives (Scheme 42) [71]. 3.2.5. Half-sandwich oxocyclohexadienyl group 10 (Ni, Pd) complexes
In solution r-bonded aryloxy complexes 137a-d exist as Treatment of the nickel chloroallyl dimer 146 with 2 equiv. of
equilibrium mixtures with PPh3 and the corresponding p-bonded the sodium salt of 2,6-di-tert-butyl-4-methylphenol, NaOAr,
species 136a-d. In the presence of phenols the equilibrium is allows the isolation of the mononuclear thermally stable red
completely shifted toward complexes with p-coordinated g5-oxocyclohexadienyl complex 147 (Scheme 47). The crystals
g5-oxocyclohexadienyl complexes 138a-d(HOAr)2 due to the for- were of low quality but the bonding mode of 147 was confirmed
mation of strong hydrogen bonds between the oxygen atom of the by X-ray structural analysis. Larger amounts of NaOAr with a
g5-OAr ligand and two molecules of HOAr. Note that unlike 137a-d longer period of time gave low yields (10–15%) of an air sensitive
complexes, r-aryloxide species which contains an electron with- product 148. Analytical and spectroscopic data were in favor with
drawing NO2 group show no tendency to dissociate to PPh3 and the structure containing both r,m- and p,g5-aryloxide ligands; the
the corresponding g5-oxocyclohexadienyl complexes. Complexes sodium cation is coordinated to the oxygen atom of the OAr groups
138a-d(HOAr)2 could also be selectively obtained in dichloro- [76].

R' R' HOAr

R O + PPh3 Ph P R O
2 NaOAr 3 OAr 2 ArOH HOAr
[(Ph3 P)2 Rh(μ-Cl)] 2 Rh Rh Rh
- NaCl Ph3 P PPh 3 - PPh Ph3 P PPh3 - PPh3 Ph 3P PPh3
135 3
136a-d 137a-d 138a-d (HOAr) 2

Ar= Ph (a), 4-MeC6H4 (b), NaOAr

2-MeC6H4 (c), 4-MeOC6H4 (d)
[(Ph 3P)3 Rh(Cl)]
128

Scheme 43. Synthesis of g5-oxocyclohexadienyl rhodium complexes 138a-d via HOAr adduct [72].
 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322 313

HOPh i i
O Pr2 Ph Pr 2
PhOH HOPh P O P
[(dippe)Rh( μ-H)] 2 Rh + Rh Rh
i
- H2 Pr 2P Pi Pr2 P H P
139 iPr iPr
2 2
140 (HOPh) 2 141

3 PhOH
[(dippe)Rh( η3-C 3 H6 )]
- C 3H 6
142

Scheme 44. Synthesis of g5-oxocyclohexadienyl rhodium complexes 140 via strong hydrogen bonds [73].

tBu

tBu Me
Me OH Me O
Me O Me
t
Bu Ag , HOMes Me
tBu
[(Ph3 P)2 Rh(N(SiMe 3) 2] Rh Pd Pd
- HN(SiMe3 )2 Ph 3P PPh3 Cl - AgCl, - MeH
143 131 149
Scheme 45. Synthesis of g -oxocyclohexadienyl rhodium complexes 131 via an
5

amide precursor 143 [74]. 150

Scheme 48. Synthesis of g5-oxocyclohexadienyl palladium complex 150 [77].

O KOH
Ir R Ir
P P
tBu MeOH tBu
2 2
144a ,b 145a ,b
R= H (a), Me (b )
Scheme 46. Synthesis of g5-oxocyclohexadienyl iridium complexes 145a,b via
alkyl C–O bond cleavage [75].
The deep red air-sensitive g5-oxocyclohexadienyl complex 150
was prepared in good isolated yield (66%) after in situ sequential
additions of silver salt and 2,4,6-trimethylphenol, HOMes, on
methyl palladium precursor 149 (Scheme 48). Suitable crystals
for X-ray crystallography were obtained which confirmed that
the mesitylato ligand coordinates in a g5-fashion with no Pd  O
interaction [77].
4. Reactivity of oxocyclohexadienyl transition metal complexes
In the previous section, it was reported that g6-phenol species
are easily deprotonated with bases to form the corresponding g5-
oxocyclohexadienyl complexes. It was then anticipated that g5-
oxocyclohexadienyl complexes could be regenerated to their corre-
sponding g6-phenol species after treatment with mineral acids HX.
Therefore, interconversion of g5-oxocyclohexadienyl transition
metal complexes to their corresponding phenol compounds, upon
protonation/deprotonation processes, has been largely exemplified
in the literature and only some selected examples will be given in
this section.
O
4.1. Reactivity of oxocyclohexadienyl ruthenium complexes
R
4.1.1. Reactivity of sandwich oxocyclohexadienyl ruthenium
complexes
In the frame of the chemistry of sandwich
g5-oxocyclohexadienyl/g6-phenol ruthenium complexes, upon
coordination, proton dissociation enables the transformation of
the A-ring in a,b-21 into the conjugated g5-oxocyclohexadienyl
form a,b-20. In the presence of NEt3, the estradiol derivatives a,
b-21 lose the phenolic character of their A-ring in favor of the cor-
responding g5-oxocyclohexadienyl form a,b-20. [25]. It was then
demonstrated that addition of HPF6 enables to regenerate the cor-
responding g6-phenol ruthenium complexes a,b-21 (Scheme 49).
In the case of g5-oxocyclohexadienyl metal complexes formed
as adducts hydrogen-bonded to the oxygen atom of the six mem-
bered ring, it was demonstrated for complex 10(HOPh)2
(Scheme 7) that this compound behave as an integral compound
in solution and in the solid state. Acidification of the adduct 10
(HOPh)2 with mineral acid liberates excess phenol and generates
the known cation complex 9 (Scheme 50) [20,27]. Addition of
MeI on 10(HOPh)2 led to the formation of the expected sandwich
anisole complex 151.
Note that treatment of base, as NEt3, removes the hydrogen-
bonded phenols in 10(PhOH)2 [26,27]. The corresponding complex
10 has been subjected to flash vacuum pyrolysis (FVP). This results
in extrusion of CO and formation of the known cyclopentadienyl
complex [Cp⁄CpRu] 152. Analogous FVT of 24a also results in
extrusion of CO, but in addition to the expected product [Cp⁄Ru
(1,2-C5tBu2H3)] 153, the corresponding isomeric complex [Cp⁄Ru

t
Bu Ar
O
t t
Bu Bu Na
2 Me ONa Ni
Me O Me O
t t
O
Bu tBu Bu Ar
[(η3 -C 3 H6 )Ni(μ -Cl)] 2 Ni Ni
146
147 148

Scheme 47. Synthesis of g5-oxocyclohexadienyl allyl nickel complexes 147 and 148 [76].
314 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322

Me OH F F F
HPF6 Me OH F O flash vacuum F F
F F pyrolysis F F
Ru Ru
Cp* - CO Cp*
O Et3 N
Ru HO 26b 155
Cp* Ru
Cp* Scheme 52. FVP of the sandwich perfluoronated g5-oxocyclohexadienyl ruthe-
α,β-20 α,β-21
nium complex 26b [32].

Scheme 49. Interconvertion of g5-oxocyclohexadienyl a,b-20/ g6-phenol a,b-21

ruthenium complexes via protonation/deprotonation processes [25].

O OH
H2
Ru Ru
Cy3 P H Cy3 P H
HOPh Cy 3P - PCy3 H
OMe O OH
MeI HOPh HOTf 38 156
Ru Ru Ru
Cp* I - 2 PhOH Cp* - 2 PhOH Cp* OTf
H2
151 10 (HOPh) 2 9
O
Scheme 50. Protonation and methylation reactions of g5-oxocyclohexadienyl
Ru
complex 10(HOPh)2 [20,27]. Cy3 P
Cy2 P
(1,3-C5tBu2H3)] 154 is formed. Note that complexes 153 and 154 39
do not interconvert under the thermolysis conditions and that no
rearrangement of recovered starting material is observed [29] Scheme 53. Hydrogenation reaction of g5-oxocyclohexadienyl ruthenium com-
(see Scheme 51). plexes 38 and 39 [38].

In an identical reaction, flash vacuum pyrolysis (FVP) of the per-

fluorinated complex 26b at 750 °C under vacuum (l04 Torr)
results in CO extrusion and formation of the pentafluorocyclopen-
tadienyl complex 155 in 20% yield, with the starting complex 26b
recovered in 60% yield [32] (see Scheme 52).
Note that flash vacuum thermolysis of partially fluorinated
complexes [RuCp⁄(g5-C5F5nHnCO)] (n = 1–4) results in extrusion
of CO and selective formation of the corresponding complexes
[Cp⁄Ru(g5-C5F5nHn)] containing the monofluorocyclopentadienyl,
1,2-difluorocyclopentadienyl, 1,3-difluorocyclo-pentadienyl, 1,2,3-
trifluorocyclopentadienyl, 1,2,4-trifluorocyclopentadienyl, and
tetrafluorocyclopentadienyl ligands [33].
4.1.2. Reactivity of half-sandwich oxocyclohexadienyl ruthenium
complexes
Very few reactions have been investigated in the area of half-
sandwich g5-oxocyclohexadienyl ruthenium complexes.
Interestingly, 38 was reacted with H2 in toluene at 80 °C to give
a dihydrido p-bonded phenol complex 156. The authors proposed
that the p-bonded g5-oxocyclohexadienyl complex 38 can be
viewed as a formal zwitterionic species which will favor the het-
erolytic addition of H2. Note that this activation of H2 is involved
in a number of hydrogenation processes. A precedent has been
described by Shvo et al. upon hydrogenation of [Ru(g4-C4Ph4CO)
(CO)2] 4b [7]. Unfortunately 156 was not isolated in a pure
form, it was contaminated with small amounts of
g5-oxocyclohexadienyl complex 38 and PCy3. The chelating
g5-oxocyclohexadienyl complex 39 was also reacted with H2 in
toluene at 80 °C. The reaction leads to a mixture of
g5-oxocyclohexadienyl complex 38 and the dihydrido p-bonded
phenol complex 156. If the reaction is carried out at room temper-
ature no reaction occurs [38] (see Scheme 53).
As demonstrated for a large number of sandwich complexes,
g5-oxocyclohexadienyl ruthenium compound 6 interconvert to
its corresponding phenol compound 157 upon protonation/depro-
tonation processes. In contrast to 6, addition of HCl on the p-alkyl
substituted g5-oxocyclohexadienyl ruthenium complex 48b led to
an exchange reaction and the corresponding chloride complex 158
is formed (Scheme 54) [44]. Note that complex 6 does not react
with carbon dioxide in boiling toluene but it reacts with carbon
monoxide at room temperature to give [Ru(CO)3(PPh3)2]. In metha-
nol the corresponding O-hydrogen bonded g5-oxocyclohexadienyl
ruthenium is formed 6HOMe.
Pioneering evidence for catalytic activity of a metal complex
incorporating an g5-oxocyclohexadienyl ligand was reported with
half-sandwich ruthenium complexes [45]. The dimeric g5-
oxocyclohexadienyl ruthenium complex 62 is effective in the
base-free redox isomerization of allylic alcohols and is able to

OH

R= H Ru Cl
Ph 3P H
R Ru
Cp* R O PPh3
O flash vacuum
HCl 157
R pyrolysis 152 Ru
Ru t Ph 3P H
Cp* - CO tBu
Bu PPh3 t
Bu O
10 R= H tBu t 6 R= H
Bu Ru
24a R= tBu Ru + Ru 48b R= iBu Ph3 P Cl
R= tBu Cp* Cp* PPh3
153 154 158

Scheme 51. FVP of sandwich g5-oxocyclohexadienyl ruthenium complexes 10 and Scheme 54. Treatment of g5-oxocyclohexadienyl hydrido ruthenium complexes 6
24a [29]. and 48b [44].
 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322 315

R2 N CHR2 CR2
O O O
N tBuOK
Ru
P Rh Rh
Ph 2 Cl Cp* Cp*

62
2 95a ,b 160a ,b
OH (0.5 mol% of Ru) O
Scheme 56. Synthesis of stable o-quinone methide rhodium complexes 160a,b
THF / 80 ºC / 5 h [58].
> 99% GC yield
91% isolated yield

Fig. 3. Isomerization of a citral-derived allylic alcohol with dimeric half-sandwich R1 OMe

g5-oxocyclohexadienyl tethered ruthenium complex 62 [45]. R2 O
MeONa
R3
operate under mild conditions with a large scope of substrates R1 Ir
(Fig. 3) [45]. The monomeric catalytically active ruthenium frag- R2 O Cp*
ment 63 of the g5-oxocyclohexadienyl ruthenium dimer 62 is R3 BF4 97a-c
structurally related to the 16-electron monoruthenium active spe- Ir
Cp*
cies 4 formed after thermal dissociation of the Shvo catalysts 2
92, 96b,c PR 3 PR3
(Fig. 1). Promising preliminary results recorded in the hydration
reaction of nitriles and in the synthesis of c-valerolactone by a R1 ,R2,R3= H O
BF4
b R1= Me, R2 = H, R3 = Me d PR3 = PMe3
hydrogenation of biomass-derived levulinic acid with tethered
c R1 = Me, R2 = Me, R3= H e PR3 = PEt3 Ir
g5-oxocyclohexadienyl ruthenium complexes 61–62 allowed one f PR3 = PMe2Ph Cp*
to anticipate that other challenging organic transformations with
161d-f
related complexes will be reported soon in catalysis.
Note that preliminary catalytic tests with the first Scheme 57. Reactivity of g5-oxocyclohexadienyl iridium complexes 92 and 96b,c
reported g5-oxocyclohexadienyl transition metal complex with nucleophiles [59,78].
[RuH(g5-C6H5O)(PPh3)2] 6 prepared by Wilkinson, Cole-Hamilton
and Young in 1976 showed also remarkable activities and proved the nucleophiles affords the g4-diene tautomers 161d-f in which
to be active in the isomerization of the model substrate the organophosphorus moieties add regioselectively at C-2
1-octen-3-ol [45]. (Scheme 57). The structure of these complexes were determined
without ambiguity by an X-ray analysis [78].
Addition of HBF4OEt2 on the g5-oxocyclohexadienyl complex
4.2. Reactivity of oxocyclohexadienyl non-ruthenium complexes 92 in a 1:1 mixture of benzene and 3-methyl-2-oxazolidinone, a
solvent with high dialectic constant, allows for direct conversion
4.2.1. Reactivity of sandwich oxocyclohexadienyl non-ruthenium of 92 into the corresponding benzene arene complex 100 with
complexes release of phenol [61] (see Scheme 58).
In situ generation of the g5-oxocyclohexadienyl iron complex
70 was achieved from the 2-trimehylsilylethoxide-protected
phenol complex 71c which was quenched with a variety of elec- 4.2.2. Reactivity of half-sandwich oxocyclohexadienyl non-ruthenium
trophiles to form the corresponding aryl ether complexes 71c,a-c complexes
(Scheme 55) [48,49]. Note that transetherification reactions have Chromium aryloxide anion 110a reacts with p-toluene-sulfonyl
been also reported with many other aryl ether iron complexes. chloride electrophile to form the corresponding p-phenyltosylate
These reactions are of synthetic interest for the construction of complex 111a in modest yield, isolated as a yellow thermally
organometallic assemblies. stable powder (Scheme 59). Note that the corresponding
Treatment of the g5-oxocyclohexadienyl complexes 95a,b with [(g6-2,6-dimethylphenyltosylate)Cr(CO)3 derivative 111b decom-
1 equiv of tBuOK led quantitatively to the formation of stable poses rapidly at ambient temperature both in solution and in the
o-quinone methide rhodium complexes 160a,b [58] (see solid state. Additions of metal electrophiles (CpFe(CO)+3 or Cp2-
Scheme 56). ZrC12) on the p-phenoxide anions 110a-c resulted in electron-
Oxocyclohexadienyl iridium species 92 and 96b,c react with transfer reactions that consume the starting arene complexes [63].
MeONa to give the neutral stable g4-diene complexes 97a-c Treatment of g5-oxocyclohexadienyl manganese complexes as
involving hapticity changes of the coordinated hydrocarbon as 117a with nucleophiles can afford the corresponding ortho
g5 ? g4. Nucleophilic attack occurs exclusively at the ortho- substituted complexes 162 which give after demetallation ortho-
position with exo-stereochemistry relative to the organometallic substituted phenols (Scheme 60). Acylation of the phenolic oxygen
unit [Cp⁄Ir] (Scheme 57) [59]. Treatment of 92 with an excess of to give 163 followed by treatment of acid led to the formation of
trialkylphosphines (PR3 = PMe3 (d), PEt3 (e), and PMe2Ph (f)) as monosubstituted g6-arene manganese complexes 164 (Scheme 60)

OR O OR
t
BuOK RX
Fe Fe Fe
Cp THF Cp THF Cp
71c 70 71a R= Me
R= CH2CH2SiMe3 159 a R= Et
b R= CH2CH=CH2
c R= SO 2-p-tol

Scheme 55. Reactivity of in situ generated g5-oxocyclohexadienyl iron complex 70 with electrophiles [48,49].
316 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322

2 OE
O H 1/ Nu Nu
HBF4 OEt2 O
2/ E H
Ir Ir + OH Mn Mn
Cp* Me Cp* L
OC L OC
N CO Nu= RMgBr, RLi CO
92 1 1 O 100
O 117a L= CO E= RX, (RCO)2O 165a-c
Scheme 58. Reactivity of g5-oxocyclohexadienyl iridium complexes 92 with HBF4- 118 L= PPh3 L= CO (a), PPh3 (b),
OEt2 [61]. 119 L= P(OMe)3 P(OMe)3 (c)

Scheme 61. Sequential addition of nucleophiles and electrophiles on g5-oxocyclo-

O OTs hexadienyl manganese complexes 117a, 118, and 119 [67].

R TsCl R
Cr Cr
OC CO - Cl OC CO
CO CO
O (HOPh) 5 OH
110a 111a HBF4
Os Os BF4
Scheme 59. Reactivity of g5-oxocyclohexadienyl chromium complex 110a with iPr P PiPr3 i Pr P PiPr 3
3 Et 2 O 3
nucleophiles [63]. H H
121 (HOPh) 5 122
O
Scheme 62. Protonation of g5-oxocyclohexadienyl osmium complex 121(HOPh)5
Nu OH
[69].
Nu H demetallation
Mn Nu
OC CO
R' HOAr
CO
O Nu= RMgBr, RLi R O
162 HOAr Ph3 P OAr
CO
Mn Rh Rh
OC CO OAc Ph3 P PPh3 Ph3P CO
CO Nu - 2 HOAr
Nu
117a 1. Nu H HBF4 138a-d (HOAr) 2 166a-d
Mn Mn BF 4
2. Ac 2O OC CO OC CO Scheme 63. Addition of CO on g5-oxocyclohexadienyl rhodium complexes 138a-d
CO CO
(HOAr)2 [72].
163 164

Scheme 60. Reactivity of g -oxocyclohexadienyl manganese complex 117a with

5

nucleophiles [66]. MeO Me

O O O
MeOH O
Ir Ir Ir
[66]. These processes have been exemplified with complexes 117b- P P P
t t t
d (Scheme 38) [66]. Bu 2 Bu 2 Bu2
The g5-oxocyclohexadienyl manganese complexes 117a, 118, 144a 167 168
and 119 react consecutively with several kinds of nucleophiles
(Nu) and electrophiles (E) to give reasonable to high yields of Scheme 64. Addition of methanol on g5-oxocyclohexadienyl vinylphosphine
double-addition products 165a-c (Scheme 61). The controlling fac- iridium complex 144a [75].

tors for the yields of 162a-c were not fully understood. The double
addition to 117a, 118, and 119 can be done in a one-pot reaction,
and Grignard reagents or RLi can be used as nucleophile and alkyl
halides or acid anhydrides can be used as electrophiles. Then, oxo-
cyclohexadienyl manganese compounds 165a-c can be treated
with Jones reagent to liberate the corresponding 1,2-
disubstituted benzenes [67].
With g5-oxocyclohexadienyl hydrido osmium complex 121
(HOPh)5 it was also demonstrated that the g6-phenol complex
122 could be regenerate with HBF4OEt2 (Scheme 62). The protona-
tion is reversible. Treatment of tetrahydrofuran solutions of 122
with 1.1 equiv of tBuOK regenerates 121 in almost quantitative
yield [69].
Note that in complex [Rh(dppe)(g5-OPh)] 127, the electrophilic
attack by CO2 is addressed onto the p-bonded aromatic ring,
resulting in the selective carboxylation of the g5-phenoxide. The
exact nature of the Rh-carboxylated compound could not be clari-
fied in detail, as the attempts to isolate it in a pure form were
unsuccessful. The phenoxy-group carboxylated in para position
was demonstrated by the acidolysis experiments with HCl. The
reaction solution showed the presence of 4-OH-benzoic acid which
clearly demonstrates that upon reaction of 127 with carbon diox-
ide, the p-bonded aryloxy-ligand is selectively carboxylated in para
position [70].
Exposure of CO on the g5-oxocyclohexadienyl rhodium com-
plexes 138a-d(HOAr)2 gave the r-bonded ayloxy complexes
166a-d [72] (see Scheme 63).
The controlled addition of MeOH on a toluene solution of
g5-oxocyclohexadienyl complex 144a resulted in the formation
of compound 168, which was isolated as a brown solid in moderate
yield. The O-bonded aryloxy complex 168 was formed via an anti-
Markovnikoff addition of MeOH to the vinyl group of the coordi-
nated vinylphosphine ligand in 167. The g5-oxocyclohexadienyl
ligand tautomerizes to a j-O-phenoxide ligand, facilitating the
j2-O,P mode of coordination of the methoxyethyldi-tert-
butylphosphine ligand in compound 168 (Scheme 64) [75].
5. Spectroscopic and X-ray analysis of oxocyclohexadienyl
ligand in transition metal complexes
5.1. Spectroscopic features of oxocyclohexadienyl ligand in transition
metal complexes
Most of the p-coordinated 6-membered g5-oxocyclohexadienyl
metal complexes described in this review have been spectroscopi-
cally fully characterized by elemental analysis, mass spectrometry,
IR and multinuclear NMR spectroscopy.
 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322 317

Infrared (IR) studies report CO vibrational modes between

1540 and 1635 cm1 characteristic of a double bond. As an exam-
ple, the tc=O frequency goes from 1542 to 1614 cm1 for [Cp⁄Ru
(g5-OC6H5)] 10 and [Cp⁄Ru(g5-OC6F5)] 26b complexes respec-
tively. These data are consistent with an g5-geometry with a
C@O carbonyl group for the 6-membered p-coordinated aryloxy
ring.
In the 1H NMR spectra, the aromatic proton resonances of the 6-
membered p-coordinated aryloxy rings are significantly shifted to
higher field as compared to the resonances of the corresponding
phenols or O-bonded aryloxy ArO- ligands [12,15] and appear in
the region of 4.1–6.2 ppm. The large upfield shift observed for
the ortho resonance, compared to the para and meta hydrogen sig-
nals, was attributed to the deformation of the aromatic ring which
becomes an g5-oxocyclohexadienyl ligand. For the carbon atoms
coordinated to the metal atom, 13C NMR data reveal a characteris-
tic upfield shift, ca. 20–40 ppm, compared to the free phenoxide
ions. The chemical shift of the carbon atom of the carbonyl group
was observed in the region of d 154–170 ppm depending on the
constraint environment or the formation of an adduct through
hydrogen bonding with residual phenol derivatives or with the
solvent.
IR and NMR analytical spectroscopic data are highly valuable to
establish the hapticity of the p-coordinated 6-membered aryloxy
rings; nevertheless, in some cases, the solid state X-ray
structure analysis is essential to definitively confirm the
g5-oxocyclohexadienyl bonding mode of the corresponding metal
complex.
Fig. 4. Schematic representation of the structure of transition metal complexes
with: a) g5-oxocyclohexadienyl and, b) g5-cyclohexadienyl type ligands.
5.2. X-ray analysis of oxocyclohexadienyl type ligands in transition
metal complexes
The solid state X-ray structures studies of transition metal com-
plexes with g5-oxocyclohexadienyl ligands, ArO, show the six
membered rings to have the carbonyl carbon C1 and the oxygen
atoms above the plane, PC2-C6, formed by the pentadienyl fragment
C2-C6 (Fig. 4). A number of g5-oxocyclohexadienyl complexes
crystallized with additional molecule with hydrogen bonding
interaction with the oxygen atom of the carbonyl function C@O
of the aryloxy ring. It induces some structural modifications but
the general structural features of the arene ligand remain. Note
that the bonding mode of some oxocyclohexadienyl type ligands
in transition metal complexes has been attributed by X-ray struc-
tural analysis, but their quality for some of them is poor and their
geometrical parameters will not be discussed in this review.

Table 1
X-ray crystallographic data of half-sandwich g5-oxocyclohexadienyl transition metal complexes.

Complexes C1-O C1-C2 C1-C6 C2-C3 C3-C4 C4-C5 C5-C6 a (°) M-C1 M-C2 M-C6 M-C3 M-C4 M-C5

1.249 1.454 1.418 1.391 1.415 1.375 1.425 15.03 2.537 2.293 2.318 2.209 2.192 2.235

1.274 1.422 1.448 1.395 1.411 1.405 1.415 15.6 2.567 2.358 2.304 2.224 2.222 2.203

1.260 1.445 1.434 1.396 1.401 1.394 1.414 12.8 2.478 2.380 2.270 2.233 2.270 2.221

1.286 1.425 1.428 1.418 1.415 1.409 1.405 14.14 2.451 2.273 2.261 2.253 2.357 2.229

1.246 1.467 1.438 1.382 1.421 1.417 1.420 8.78 2.672 2.326 2.239 2.113 2.164 2.334

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318 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322

Table 1 (continued)

Complexes C1-O C1-C2 C1-C6 C2-C3 C3-C4 C4-C5 C5-C6 a (°) M-C1 M-C2 M-C6 M-C3 M-C4 M-C5

1.249 1.438 1.453 1.392 1.408 1.405 1.405 13.84 2.582 2.418 2.278 2.320 2.257 2.217

1.278 1.415 1.421 1.384 1.404 1.372 1.408 8.3 2.542 2.474 2.298 2.327 2.253 2.295

1.239 1.481 1.478 1.393 1.427 1.401 1.425 23.57 2.666 2.478 2.282 2.310 2.304 2.268

1.258 1.471 1.455 1.401 1.394 1.411 1.413 14.96 2.587 2.346 2.405 2.274 2.258 2.279

1.267 1.453 1.430 1.415 1.396 1.410 1.415 11.13 2.492 2.216 2.343 2.231 2.299 2.266

1.230 1.499 1.466 1.378 1.422 1.427 1.395 4.62 2.589 2.469 2.447 2.353 2.218 2.344

1.239 1.453 1.453 1.390 1.402 1.402 1.390 21.31 2.541 2.236 2.236 2.147 2.140 2.147

1.239 1.435 1.463 1.395 1.426 1.401 1.386 13.29 2.492 2.241 2.267 2.161 2.153 2.179

Intra-ring C–C bond distances and M-C bond lengths of the pen-
tadienyl C2-C6 carbon atoms, as well as the rather long M–C1 bond
distance (2.337–2.672 Å), compare well with transition metal com-
plexes where a cyclohexadienyl ligand is described to be linked in a
g5-coordination mode (Fig. 4, b)) [79]. All these structural features
result in the displacement of the metal atom from the centroid of
the ring toward C4 carbon atom and clearly demonstrated the pen-
tadienyl nature of the p-coordinated phenolate species, ArO- with
the CO bond tilted from the C2-C6 plane. The C–O bond length in
transition metal complexes with g5-oxocyclohexadienyl ligands,
ArO, ranges from 1.230 to 1.255 Å, and from 1.249 to 1.286 Å
when hydrogen bonding interaction occurs with the oxygen atom.
These distances are closer to the carbonyl group C@O double-bond
distance of benzoquinone (1.22 Å) than a normal phenolic C–O
bond distance (1.35–1.37 Å). This indicates that the C–O bond of
g5-oxocyclohexadienyl moiety, ArO, has substantial double-
bond character.
All these structural aspects in the solid state indicate that the p-
bonded aryloxy rings possess g5-oxocyclohexadienyl character.
This is best explained in terms of a large contribution from reso-
nance structure B (Fig. 2) (see Tables 1 and 2).
6. Conclusions
In the early days of coordination chemistry, 6-membered ring
aryloxide type ions, ArO, have been used as robust ‘‘r-oxygen
pseudohalide” ligands. These species, ArO, are sterically and elec-
tronically tunable anionic donors in transition-metal catalysis.
 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322 319

Table 2
X-ray crystallographic data of sandwich g5-oxocyclohexadienyl transition metal complexes.

Complexes C1-O C1-C2 C1-C6 C2-C3 C3-C4 C4-C5 C5-C6 a (°) M-C1 M-C2 M-C6 M-C3 M-C4 M-C5

1.285 1.415 1.432 1.410 1.384 1.386 1.401 7.36 2.337 2.211 2.202 2.186 2.206 2.191

1.255 1.471 1.464 1.417 1.397 1.404 1.417 18.99 2.555 2.295 2.301 2.192 2.184 2.196

1.254 1.444 1.459 1.426 1.405 1.413 1.412 18.38 2.471 2.216 2.249 2.208 2.256 2.220

1.283 1.435 1.444 1.409 1.409 1.409 1.423 11.42 2.414 2.240 2.237 2.193 2.198 2.204

1.234 1.474 1.422 1.393 1.419 1.428 1.399 13.81 2.475 2.293 2.241 2.239 2.206 2.207

1.194 1.463 1.475 1.390 1.432 1.416 1.378 16.22 2.497 2.233 2.221 2.230 2.241 2.194

1.149 1.478 1.523 1.432 1.447 1.477 1.459 23.03 2.575 2.193 2.244 2.245 2.250 2;220

1.230 1.454 1.448 1.414 1.417 1.436 1.334 17.98 2.520 2.221 2.242 2.200 2.169 2.210

1.225 1.471 1.476 1.418 1.405 1.440 1.408 16.52 2.554 2.338 2.225 2.222 2.207 2.195

1.246 1.471 1.470 1.401 1.405 1.384 1.400 9.51 2.414 2.217 2.252 2.081 2.056 2.112

1.283 1.417 1.421 1.400 1.389 1.384 1.429 6.69 2.314 2.172 2.159 2.059 2.051 2.050

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320 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322
Table 2 (continued)
Complexes C1-O C1-C2 C1-C6 C2-C3 C3-C4
1.248 1.469 1.473 1.414 1.407
1.245 1.480 1.480 1.416 1.412
tunable arene ring ligand
Rn basic site
possibility for O transition metal complexes the oxygen atom of the cyclic ligand
well-defined "cage"
tethered backbone
M for substrates
modifications
Z g5-oxocyclohexadienyl transition metal complexes to interconvert
metal
Y acidic site
modulation of the electronic and steric
properties of Z and Y ligands
Fig. 5. Schematic representation of an g5-oxocyclohexadienyl bifunctional transi-
tion metal catalyst.
Since the seminal work by Cole-Hamilton, Young and Wilkinson
in 1976, the non-innocent nature of aryloxide type ligands, ArO,
was indicated in the p-coordination mode adopted by the arene
ring. The electronic description of the 6-membered p-
coordinated aryloxide ligand, A and B (Fig. 2), in transition metal
complexes is doubtless related with the nature of the metal and
its side ligands. It was rapidly proposed that 6-membered p-
coordinated aryloxide type rings, ArO-, are usually referred to as
g5-oxocyclohexadienyl ligands B in transition metal complexes.
For some complexes, the A form (Fig. 2) was proposed for the elec-
tronic description of the p-coordinated aryloxide ring on the basis
of their solubility in water or from spectroscopic data recorded in
solution. Even if it is sometime difficult to assign the hapticity
for the aryloxy ring ligand, ArO, X-ray data allowed one to attri-
bute an g5-geometry for the oxocyclohexadienyl ligand coordi-
nated to a transition metal fragment. For the large majority of
complexes, according to experimental analytical data recorded in
the liquid and solid phases, the electronic structure of the
p-coordinated 6-membered aryloxide ligands in transition metal
complexes is best described by the g5-oxocyclohexadienyl
tautomeric form B (Fig. 2). Note that some studies demonstrate
that the monomeric j 1-O aryloxy bonding mode precedes the for-
mation of the corresponding g5-oxocyclohexadienyl complex.
A large number of experimental and computed electronic data
have been reported in the literature to measure, describe, rational-
ize and predict the relative electron donor/acceptor properties of a
wide variety of ligands with very diverse bonding mode in coordi-
nation chemistry [80]. For p-arene type ligands very few studies
have been reported [81]. Theoretical investigations on the topolog-
ical analysis of the electronic structure of g5-oxocyclohexadienyl
transition metal complexes are still missing. Combined experimen-
tal/theoretical approach should allow one to get a more precise
insight into the metal-carbon and carbon-oxygen bonding for a
better electronic description of g5-oxocyclohexadienyl ligands.
C4-C5 C5-C6 a (°) M-C1 M-C2 M-C6 M-C3 M-C4 M-C5
1.404 1.411 16.25 2.442 2.210 2.211 2.103 2.122 2.099
1.412 1.416 1.13 2.436 2.330 2.330 2.182 2.089 2.182
The synthesis of g5-oxocyclohexadienyl transition metal com-
plexes can be easily achieved via a broad range of chemical path-
ways. During the synthetic course of the g5-oxocyclohexadienyl
was prompted to provide a hydrogen bond interaction with various
substrates. The studies reported to date emphasized the ability of
to the corresponding phenol compounds upon protonation/depro-
tonation processes.
This review points out the potential of g5-oxocyclohexadienyl
transition metal complexes for applications in various fields as in
catalysis and medicinal chemistry to name as a few. Coordinatively
unsaturated g5-oxocyclohexadienyl transition metal complexes
(Fig. 5) may be considered as ‘‘bifunctional catalysts” precursors
which have been lately the subject of growing interest [82]. It is
important to note that in marked contrast to the Shvo type cata-
lysts, g5-oxocyclohexadienyl transition metal complexes are both
sterically and electronically tunable on the metal center and on
the p-coordinated cyclic ligand. It will be then possible to optimize
the metal-g5-oxocyclohexadienyl ligand cooperativity for catalysis
and to incorporate in the g5-oxocyclohexadienyl transition metal
structure a chirality element for asymmetric chemical transforma-
tions. We therefore anticipate that non-tethered and tethered of
half-sandwich g5-oxocyclohexadienyl metal complexes can be
considered as promising new catalysts and deserve further
fundamental experimental research work with respect to
structure/activity relationships. The pioneering results obtained
so far with g5-oxocyclohexadienyl ruthenium metal complexes
in catalysis [45] pave the way for future investigations in
challenging organic chemical transformations. The development
of g5-oxocyclohexadienyl ligands in coordination chemistry goes
through a deeper understanding on the theoretical and spectro-
scopic features of their corresponding transition metal complexes.
A large amount of fundamental data still need to be collected.
For the above-mentioned reasons, we can expect that
g5-oxocyclohexadienyl transition metal complexes, as well as
their rare thio-, seleno-, and imino-cyclohexadienyl congeners
[52,83a–e], have a long way to go in coordination chemistry
extending their domain of applications.
Acknowledgements
We are grateful to the successive Directors of the Laboratoire de
Chimie de Coordination. We warmly thank the technical and
administrative staff of the laboratory for their support in our daily
research activities. Our studies were supported by the CNRS, the
Universite Paul Sabatier (Toulouse) and the French Ministry of
Education and Research.
 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322 321

References [21] U. Koelle, C. Weibschädel, U. Englert, J. Organomet. Chem. 490 (1995) 101.
[22] (a) J.M. Wolff, W.S. Sheldrick, Chem. Ber. 130 (1997) 981;
(b) R. Stodt, S. Gencaslan, A. Frodl, C. Schmidt, W.S. Sheldrick, Inorg. Chem.
[1] (a) R.H. Crabtree, The Organometallic Chemistry of the Transition Metals, John
Acta 355 (2003) 242.
Wiley and Sons, Wiley Interscience, New York, 2014;
[23] M. Kimura, M. Morita, H. Mitani, H. Okamoto, K. Satake, S. Morosawa, Bull.
(b) B.D. Gupta, Anil J. Elias, Basic Organometallic Chemistry: Concepts,
Chem. Soc. Jpn. 65 (1992) 2557.
Syntheses, and Applications of Transition Metals, CRC Press, 2010;
[24] D. Vichard, M. Gruselle, H. El Amouri, G. Jaouen, J. Chem. Soc., Chem. Commun.
(c) Ruthenium in Catalysis, P. H. Dixneuf, C. Bruneau, (Eds.) Topics in
(1991) 46.
Organometallic Chemistry.
[25] H. El Amouri, A. Vessières, D. Vichard, S. Top, M. Gruselle, G. Jaouen, J. Med.
[2] (a) H. Xu, R. Chen, Q. Sun, W. Lai, Q. Su, W. Huang, X. Liu, Chem. Soc. Rev. 43
Chem. 35 (1992) 3130.
(2014) 3259, and references cited therein;
[26] B. Chaudret, X. He, Y. Huang, J. Chem. Soc., Chem. Commun. (1989) 1844.
(b) Terpyridine-Based Materials: For Catalytic, Optoelectronic and Life Science
[27] U. Koelle, M.H. Wang, G. Raabe, Organometallics 110 (1991) 2573.
Applications, U. S. Schubert, A. Winter, G. R. Newkome (Eds.), 2011.;
[28] K. Bucken, U. Koelle, R. Pasch, B. Ganter, Organometallics 15 (1996) 3095.
(c) K. Kalyanasundaram, M. Grätzel, Coord. Chem. Rev. 177 (1998) 347.
[29] R.P. Hughes, A.S. Kowalski, Organometallics 17 (1998) 270.
[3] (a) G. Palermo, A. Magistrato, T. Riedel, T. von Erlach, C.A. Davey, P.J. Dyson, U.
[30] S.D. Loren, B.K. Campion, R.H. Heyn, T. Don Tilley, B.E. Bursten, K.W. Luth, J.
Rothlisberger, Chem. Med. Chem. 11 (2016) 1199;
Am. Chem. Soc. 111 (1989) 4712.
(b) G. Eskici, P.H. Axelsen, Biochemistry 51 (2012) 6289, and references cited
[31] R.P. Hughes, X. Zheng, A.L. Rheingold, R.L. Ostrander, Organometallics 13
therein;
(1994) 1567.
(c) Ligand Design in Medicinal Inorganic Chemistry, T. Storr Ed., John Wiley &
[32] O.J. Curnow, R.P. Hughes, J. Am. Chem. Soc. 114 (1992) 5895.
Sons, Hoboken, 2014.
[33] R.P. Hughes, X. Zheng, C.A. Morse, O.J. Curnow, J.R. Lomprey, A.L. Rheingold, G.
[4] (a) T.J. Kealy, P.L. Pauson, Nature 168 (1951) 1039;
P.A. Yap, Organometallics 17 (1998) 457.
(b) S.A. Miller, J.A. Tebboth, J.F. Tremaine, J. Chem. Soc. (1952) 632.
[34] U. Koelle, A. Hornig, U. Englert, Organometallics 13 (1994) 4064.
[5] G. Wilkinson, M. Rosenblum, M.C. Whiting, R.B. Woodward, J. Am. Chem. Soc.
[35] T. Kondo, F. Tsunawaki, Y. Ura, K. Sadaoka, T. Iwasa, K. Wada, T.-A. Mitsudo,
74 (1952) 2125.
Organometallics 24 (2005) 905.
[6] (a) M.-H. Delville, Inorg. Chim. Acta 291 (1999) 1;
[36] R. Obeso Rosete, D. Cole-Hamilton, G. Wilkinson, J. Chem. Soc. Dalton (1979)
(b) M. Green, I.R. Butler, Organometallic Chemistry, 28(28), (2006) 455 and
1618.
references cited therein.
[37] K. Osakada, K. Ohshiro, A. Yamamoto, Organometallics 10 (1991) 404.
[7] (a) Y. Blum, Y. Shvo, Isr. J. Chem. 24 (1984) 144;
[38] M.L. Christ, S. Sabo-Etienne, G. Chung, B. Chaudret, Inorg. Chem. 33 (1994)
(b) Y. Blum, D. Czarkie, Y. Rahamin, Y. Shvo, Organometallics 4 (1985) 1459;
5316.
(c) Y. Shvo, D. Czarkie, D.F. Chodosh, J. Am. Chem. Soc. 108 (1986) 7400.
[39] M.C. MacInnis, R. McDonald, M.J. Ferguson, S. Tobisch, L. Turculet, J. Am. Chem.
[8] (a) M.C. Warner, C.P. Casey, J.-E. Backvall, Top. Organomet. Chem. 37 (2011)
Soc. 133 (2011) 13622.
85;
[40] K. Abdur-Rashid, T. Fedorkiw, A.J. Lough, R.H. Morris, Organometallics 23
(b) B.L. Conley, M.K. Pennington-Boggio, E. Boz, T.J. Williams, Chem. Rev. 110
(2004) 86.
(2010) 2294, and references therein;
[41] J.L. Snelgrove, J.C. Conrad, M.D. Eelman, M.M. Moriarty, G.P.A. Yap, D.E. Fogg,
(c) C.P. Casey, H. Guan, Organometallics 31 (2012) 2631;
Organometallics 24 (2005) 103.
(d) X. Dou, T. Hayashi, Adv. Synth. Catal. 358 (2016) 1054.
[42] J.N. Coalter III, J.C. Huffman, W.E. Streib, K.G. Caulton, Inorg. Chem. 39 (2000)
[9] Comprehensive Organometallic Chemistry III (2007), Volume 5–8, D.M., P.
3757.
Mingos, R. H. Crabtree Eds.
[43] G. Ferrando-Miguel, P. Wu, J.C. Huffman, K.G. Caulton, New J. Chem. 29 (2005)
[10] Transition Metal Arene p-Complexes in Organic Synthesis and Catalysis.
193.
Topics in Organometallic Chemistry, 7. Edited by E.P. Kündig. Springer-Verlag:
[44] J.L. Snelgrove, J.C. Conrad, G.P.A. Yap, D.E. Fogg, Inorg. Chim. Acta 345 (2003)
Berlin, Heidelberg, New York. 2004.
268.
[11] (a) E.O. Fischer, C. Elschenbroich, Chem. Ber. 103 (1970) 162;
[45] M. Kechaou-Perrot, L. Vendier, S. Bastin, J.-M. Sotiropoulos, K. Miqueu, L.
(b) M.A. Bennett, Coord. Chem. Rev. 166 (1997) 225.
Menendez-Rodríguez, P. Crochet, V. Cadierno, A. Igau, Organometallics 33
[12] (a) Ruthenium in Organic Synthesis; Murahashi, S.-I., Ed.; Wiley-VCH:
(2014) 6294.
Weinheim, 2004.;
[46] M. Aresta, I. Tommasi, C. Dileo, A. Dibenedetto, M. Narracci, J. Ziolkowski, A.
(b) Ruthenium Catalysts and Fine Chemistry, C. Bruneau, P. H. Dixneuf Eds.,
Jezierski, Can. J. Chem. 79 (2001) 570.
Springer: Berlin, 2004.
[47] J.F. Helling, W.A. Hendrickson, J. Organomet. Chem. 168 (1979) 87.
[13] (a) B. Therrien, T.R. Ward, Angew. Chem. Int. Ed. 38 (1999) 405;
[48] F. Moulines, L. Djakovitch, M.-H. Delville-Desbois, F. Robert, P. Gouzerh, D.
(b) B. Cetinkaya, S. Demir, I. Ozdemir, L. Toupet, D. Semeril, C. Bruneau, P.H.
Astruc, J. Chem. Soc., Chem. Commun. (1995) 463.
Dixneuf, Chem. Eur. J. 9 (2003) 2323;
[49] M.S. Holden, A.D. Brosius, M.A. Hilfiker, E.J. Humbert, Tet. Lett. 41 (2000) 6275.
(c) J.H. Rigby, M.A. Kondratenko, Top. Organometal. Chem. 7 (2004) 181;
[50] V. Sartor, S. Nlate, J.-L. Fillaut, L. Djakovitch, F. Moulines, V. Marvaud, F. Neveu,
(d) M. Ito, Y. Endo, T. Ikariya, Organometallics 27 (2008) 6053;
J.-C. Blais, J.-F. Létard, D. Astruc, New J. Chem. 24 (2000) 351.
(e) D. Arquier, L. Vendier, K. Miqueu, J.-M. Sotiropoulos, S. Bastin, A. Igau,
[51] M. Wallasch, G. Wolmershiiuser, H. Sitzmann, Angew. Chem. Int. Ed. 44 (2005)
Organometallics 28 (2009) 4945;
2597.
(f) P. Kacer, M. Kuzma, E. Leitmannova, L. Cerveny, Organometallic
[52] M.D. Walter, P.S. White, Inorg. Chem. 51 (2012) 11860.
Compounds, Ed. H. F Chin, Nova Science Publishers Inc, Southport, UK, 2010,
[53] G. Fairhurst, C. White, J. Organomet. Chem. 160 (1978) Cl7.
pp. 373–401.;
[54] C.-X. Yuan, K.-D. Zhou, X.-P. Xu, Y. Zhang, S. Jun, Polyhedron 87 (2015) 245.
(g) V. Parekh, J.A. Ramsden, M. Wills, Catal. Sci. Technol. 2 (2012) 406.
[55] C. White, S.J. Thompson, P.M. Maitlis, J. Organomet. Chem. 127 (1977) 415.
[14] D. Cole-Hamilton, R.J. Young, G. Wilkinson, J. Chem. Soc., Dalton (1976) 1995.
[56] J. Le Bras, M.N. Rager, Y. Besace, H. Amouri, J. Vaissermann, Organometallics 16
[15] (a) J.P. Collman, L.S. Hegedus, J.R. Norton, R.G. Finke, Principles and
(1997) 1765.
Applications of Organotransition Metal Chemistry, 2nd ed., University
[57] H. El-Amouri, M. Gruselle, P.A. Jackson, G. Jaouen, J. Vaissermann,
Science Books, Mill Valley, CA, 1987;
Organometallics 9 (1990) 2871.
(b) G.W. Parshall, S.D. Ittel, Homogeneous Catalysis: The Application and the
[58] H. Amouri, J. Vaissermann, M.N. Rager, D.B. Grotjahn, Organometallics 19
Chemistry of Catalysis by Soluble Transition Metal Complexes, 2nd ed., Wiley-
(2000) 5143.
Interscience, New York, 1992;
[59] (a) J. Le Bras, H. El Amouri, Organometallics 15 (1996) 5706;
(c) R.H. Crabtree, The Organometallic Chemistry of Transition Metals, 4nd ed.,
(b) H. Amouri, J. Vaisserman, M. N. Rager, Y. Besace, 38 (1999) 1211.
Wiley-Interscience, New York, 2005.
[60] A.J.M. Miller, W. Kaminsky, K.I. Goldberg, Organometallics 33 (2014) 1245.
[16] (a) A.F.A. Peacock, P.J. Sadler, Chem. Asian J. 3 (2008) 1890;
[61] E.M. D’Amato, C.N. Neumann, T. Ritter, Organometallics 34 (2015) 4626.
(b) B.S. Murray, M.V. Babak, C.G. Hartinger, P.J. Dyson, Coord. Chem. Rev. 306
[62] W.S. Trahanovsky, R.A. Hall, J. Am. Chem. Soc. 99 (1977) 4850.
(2016) 86.
[63] J.A. Heppert, T.J. Boyle, F. Takusagawa, Organometallics 8 (1989) 461.
[17] (a) T.B. Rauchfuss, K. Severin, Edited by J.L. Atwood, J.W. Steed, Organic
[64] J.T. Henthorn, S. Lin, T. Agapie, J. Am. Chem. Soc. 137 (2015) 1458.
Nanostructures (2008) 179.;
[65] K.K. Bhasin, W.G. Balkeen, P.L. Pauson, J. Organomet. Chem. 204 (1981) C25.
(b) R.N. Grimes, Coord. Chem. Rev. 143 (1995) 71;
[66] H. Seo, S.-G. Lee, D.M. Shin, B.K. Hong, S. Hwang, D.S. Chung, Y.K. Chung,
(c) M.A. Petrukhina, Coord. Chem. Rev. 251 (2007) 1690;
Organometallics 21 (2002) 3417.
(d) Chirality in Transition Metal Chemistry: Molecules, Supramolecular
[67] Si-G. Lee, J.-A. Kim, Y.K. Chung, T.-S. Yoon, N.-J. Kim, W. Shin, J. Kim, K. Kim,
Assemblies and Materials, H. Amouri, M. Gruselle Eds., 2009, Wiley.
Organometallics 14 (1995) 1023.
[18] (a) Note that Atwood and Ishii reported transition metal complexes with calix
[68] D. Morvan, T.B. Rauchfuss, S.R. Wilson, Organometallics 28 (2009) 3161.
[4]arene ligands where phenolate rings are p -bounded to a metal fragment
[69] M.A. Esteruelas, J. García-Raboso, M. Olivàn, Organometallics 30 (2011) 3844.
and in close p-interaction with an anion or a solvating molecule located in the
[70] M. Aresta, A. Dibenedetto, M. Pascale, E. Quaranta, I. Tommasi, J. Organomet.
cavity surrounded by the aryl rings. These species are beyond the scope of this
Chem. 605 (2000) 143.
review. J.W. Steed, R.K. Juneja, J.L. Atwood Angew. Chem., Int. Ed. Engl. 33
[71] L. Dahlenburg, N. Höck, J. Organomet. Chem. 284 (1985) 129.
(1994) 2456;
[72] V.F. Kuznetsov, G.P.A. Yap, C. Bensimon, H. Alper, Inorg. Chim. Acta 280 (1998)
(b) Y. Ishii, K.-I. Onaka, H. Hirakawa, K. Shiramizu, Chem. Commun. (2002)
l72.
1150.
[73] M.D. Fryzuk, M.-L. Jang, T. Jones, F.W. Einstein, Can. J. Chem. 64 (1986) 174.
[19] M.A. Bennett, T.W. Matheson, J. Organomet. Chem. 175 (1979) 87.
[74] B. Çetinkaya, P.B. Hitchcock, M.F. Lappert, S. Torroni, J.L. Atwood, W.E. Hunter,
[20] X.D. He, B. Chaudret, F. Dahan, Y.-S. Huang, Organometallics 10 (1991) 970.
M.J. Zaworotko, J. Organomet. Chem. 188 (1980) C31.
322 A. Igau / Coordination Chemistry Reviews 344 (2017) 299–322
[75] M.V. Jimenez, I.I. Rangel-Salas, F.J. Lahoz, L.A. Oro, Organometallics 27 (2008)
4229.
[76] J. Càmpora, M.L. Reyes, T. Hackl, A. Monge, C. Ruiz, Organometallics 19 (2000)
2950.
[77] A. Klein, A. Dogan, Organometallics 21 (2002) 2340.
[78] J. Le Bras, H. Amouri, J. Vaissermann, Inorg. Chem. 37 (1998) 5056.
[79] (a) F. Rose-Munch, E. Rose, Org. Biomol. Chem. 9 (2011) 4725;
(b) F.H. Allen, Acta Crystallogr. B 58 (2002) 380;
(c) R.D. Pike, D.A. Sweigart, Coord. Chem. Rev. 187 (1999) 183;
(d) M.F. Semmelhack, A. Chlenov, Top. Organomet. Chem. 7 (7) (2004) 43.
[80] (a) D. Setiawan, R. Kalescky, E. Kraka, D. Cremer, Inorg. Chem. 55 (2016) 2332;
(b) A.B.P. Lever, Coord. Chem. Rev. 254 (2010) 1397;
(c) F. Zobi, Inorg. Chem. 49 (2010) 10370;
(d) L. Perrin, E. Clot, O. Eisenstein, J. Loch, R.H. Crabtree, Inorg. Chem. 40
(2001) 5806.
[81] (a) S. Lu, V.V. Strelets, M.F. Ryan, W.J. Pietro, A.B.P. Lever, Inorg. Chem. 35
(1996) 1013;
(b) M.F.C. Guedes da Silva, A.J.L. Pombeiro, Electrochim. Acta 82 (2012) 478.
[82] (a) R.H. Morris, Chem. Rev. 116 (2016) 8588;
(b) P.A. Dub, J.C. Gordon, Dalton Trans. 45 (2016) 6756;
(c) A.M. Robinson, J.E. Hensley, J.W. Medlin, ACS Catal. 6 (2016) 5026.
[83] (a) J.F. Helling, W.A. Hendrickson, J. Organomet. Chem. 168 (1979) 87;
(b) J.-P. Tranchier, J. Dubarle-Offner, L. Peyroux, G. Gontard, T. Riedel, P.J.
Dyson, H. Amouri, Synlett 26 (2015) 1563;
(c) M. Yuki, Y. Miyake, Y. Nishibayashi, Organometallics 29 (2010) 4148;
(d) T. Komuro, T. Matsuo, H. Kawaguchi, K. Tatsumi, J. Am. Chem. Soc. 125
(2003) 2070;
(e) P.L. Pauson, J.A. Segal, J. Chem. Soc. Dalton (1975) 1677.