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Article history:
Received 4 August 2014
Received in revised form 9 September 2014
Accepted 14 September 2014
Available online 28 September 2014
a b s t r a c t
The synthesis of iridium dodecacarbonyl cluster derivatives Ir4(CO)12 with donor ligand such as amine,
phosphites, hydrido and cyclic mono and dioxycarbene, NMR and X-ray characterization and uxional
behavior study in solution at variable temperature is briey reviewed.
2014 Elsevier B.V. All rights reserved.
Keywords:
Iridium clusters
Carbonyl
Intramolecular dynamic
Augusto Tassan initiated its research activity in the Chemistry Department of the Venice University. He then moved to the University of Padova,
Industrial Chemistry Institute, under the supervision of Prof. R. Ros and R.A. Michelin, and collaborating with the Prof. R. Roulet of EPFL in Lausanne.
His research focuses on the synthesis of new organometallic platinum and iridium clusters, with particular interest on NMRcharacterization
Mirto Mozzon took a degree of Industrial Chemistry at the University of Padova with full marks. He became then CNR researcher in the group headed
by Prof. U. Belluco, and nally researcher at the University of Padova, under the supervision of Prof. R. A. Michelin. He is now Associate Professor. He
maintained a research cooperation whit Prof. A.J.L. Pombeiro at Instituto Superior Tecnico in Lisbon. He coauthored about 80 papers published on
peerreviewed international journals in Inorganic and Organometallic Chemistry. He also lled 4 International Patents and written 2 students book.
92
Giacomo Facchin studied chemistry at the Universit degli Studi di Padova (Italy) and completed his PhD in 1979. After a post doc term with Prof. R.J.
Angelici at the Iowa State University he joined the Italian National Research Council (CNR) where is currently Senior Researcher at the Istituto per
lEnergetica e le Interfasi (IENI). His scientic activity mainly focuses on organometallic and coordination chemistry, nanostructurated materials and
materials containing metallic nanoparticles.
Alessandro Dolmella entered the Department of Pharmaceutical and Pharmacological Sciences in 1990 to work in the research group headed by
Prof. M. Nicolini, studying radiopharmacy and computational chemistry. He is presently interested in bioinorganic and coordination chemistry, with a
special emphasis on transition metals complexes.
Serena Detti graduated in chemistry at the University of Pisa in 1996, under the supervision of Prof. F. Calderazzo and G. Pampaloni. She received her
PhD in Chemistry at the Swiss Federal Institute of Technology of Lausanne in 2002, working in the group of Prof. R. Roulet in the eld of metals
carbonyl clusters. She worked at the Italian forensic science service and later she devoted to research on nanotechnology, studying potential
interactions of metal nanostructures and the environment.
Contents
1.
2.
3.
4.
5.
6.
7.
8.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
CO-enrichment of tetrairidium carbonyl clusters .
Diamine derivatives . . . . . . . . . . . . . . . . . . . . . . . . . .
Monoamine derivatives . . . . . . . . . . . . . . . . . . . . . . .
Hydrido derivatives . . . . . . . . . . . . . . . . . . . . . . . . . .
Cyclic mono and dioxycarbene derivatives. . . . . . . .
Phosphites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Intramolecular dynamics of [Ir4(CO)12] derivatives .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
13
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1. Introduction
The chemistry of iridium carbonyls, notably, the chemistry of
clusters derived from Ir4(CO)12, were developed along various
research lines. Among the investigated topics, we can mention
the stereochemistry of the ligands [1], the uxional processes
occurring in solution [2], the studies on the kinetics of carbonyl
substitution reactions [3], the modellisation of metal surfaces for
absorption reactions of unsaturated substrates [4], the use of
such materials as catalysts or precursors in the hydrogenation
processes of hydroformylation of unsaturated organic molecules
[5].
Along with these perspectives, Garlaschelli and co-workers [6]
prepared the starting complex Ir4(CO)12 from IrCl3nH2O in
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92
93
93
94
94
96
98
99
102
CO
CO
93
In the rst step, the substitution reaction follows a secondorder kinetics law. It is characterized by an associative mechanism,
and three of the (previously) all terminal CO undergo a structural
rearrangement that transforms them into bridging CO units on
the basal iridium atoms. The following two steps have an associative-to-dissociative substitution mechanism. Factors as basicity
and the bulkness of the incoming ligand do not vary the process
kinetics [3].
Mono- or di-substituted derivatives of Ir4(CO)12 cannot instead
be isolated by direct synthesis from the tetrairidium complex,
because of its insolubility in common organic solvents and also
because the reaction requires high temperatures (80120 C).
Accordingly, alternative routes had to be sought. An opportunity,
although with low yields, is given by the reduction of Ir(CO)2(H2NC6H4Me-p)Cl by zinc metal in the presence of carbon monoxide
and the ligands [8]; another one is offered by the reaction of Ir4H(CO)11 with the appropriate ligands [9].
Still another possibility was explored by Chini et al., who prepared the anionic complexes of the type [Ir4(CO)11X] (X = Br or
I) [10]. Since the latter are soluble and more reactive than iridium
dodecacarbonyl, they can undergo replacement reactions of a CO
with several ligands, including PF3 and SO2 [11], olen [12], phosphines [13], arsines [14], yielding various complexes.
In the following sections, we provide a brief account on the synthesis, characterization and dynamic behavior of new tetrairidium
clusters with H-, N-, P-, and C-donor ligands derived from Ir4(CO)12.
2.
13
A2
b 11A1
0:16743
12
Further A3, A4, . . . Ax values can then be calculated from the following Eq. (4):
Ax
b 11Ak1
12
k 1; 2; 3; . . .
Ak f Ak1
The molecular structure and the stereochemistry of metal carbonyl derivatives might be investigated by means of 13C NMR analysis. However, a problem arises because the exchange reactions do
not always occur with free 13CO; while for some metal carbonyl
clusters, such as Co4(CO)12 and Rh4(CO)12, this exchange is easy,
the reaction involving Os3(CO)12 and Ir4(CO)12 occur only with
more difculty. The main obstacle is the low solubility of the clusters, which forces the exchange reactions to take place in heterogeneous phase and makes them extremely slow, even at high
pressures and high temperatures.
Tassan and co-workers have reported [15] two simple procedures to make the 13CO exchange process easier. The rst one
involves the use of anionic clusters; the second one requires the
use of the well-known decarbonylating agent trimethylamine-Noxide, Me3NO [1618], in the presence of free 13CO.
The rst method (a two-step process) is illustrated in Scheme 1.
At the beginning, as reported by Chini et al. [10], the reaction of
Ir4(CO)12 with NEt4I in THF at 70 C leads to the formation of the
anionic iridium tetracarbonyl [Ir4(CO)11I]. The second step, the
displacement of iodide by 13CO, occurs in THF at room temperature
and affords the enriched Ir4(CO)12 cluster.
Both reactions occur with more than 90% yield. The degree of
the rst enrichment A1 is given by the molar fraction of coordinated 13CO and can be calculated from Eq. (1) below:
A1
b 11A0
0:09266
12
13
13
"
m12 CO m13 CO
l13 CO
1
m13 CO
l12 CO
!#1=2
7
3. Diamine derivatives
13
94
[NEt4][Ir4(CO)11X]
+ (N-N) -AgX
[Ir4(CO)11{1-(N-N)}]-
-30C
R.T.
1/2 Ir4(CO)10{2-(N-N)} + 1/2 Ir4(CO)12 + 1/2 (N-N)
Scheme 3. Synthesis of diamine derivatives of tetrairidium dodecacarbonyl. (N-N)
= 1,10-phenantroline (1); 4,7-dimetylphenantroline (2); 5,6-dimetylphenantroline
(3); 3,4,7,8-tetrametylphenantroline (4); 2,20 -dipiridine (5); 4,40 -dimetyl-2,20 -dipiridine (6).
e
g
L
L
d
b
d
c
Fig. 1. Proposed structure for the diamine derivatives. (L-L = N-N).
4. Monoamine derivatives
The work on diamino ligands was extended by preparing complexes with monoamine [21], notably, with pyridine (7), 4-methylpyridine (8), 4-ter-buthylpyridine (9), 3,5-dimethylpyridine (10)
and 3,4-dimethylpyridine (11). In this case, [Ir4(CO)11Br] reacts
readily with an excess of aromatic monoamine and one equivalent
of AgBF4 in CH2Cl2 at 25 C. The products are obtained with
6071% yield, after recrystallization from a CH2Cl2/MeOH mixture.
Since in the IR spectrum there are no bands due to bridging carbonyls, this complex shows in solution and solid state a symmetry
with only terminals CO ligands. At 173 K the 13C NMR shows that
the apicals CO are already slowly exchanging and at 203 K the only
uxional mechanism observed arises from the rotation of apical
carbonyls.
The crystal structure of [PPN][Ir4(CO)10(l3-(Ph2P)2CH)] shows
Cs symmetry, with all terminals CO and with the ligand [(Ph2P)2-
95
d
c
d
a
f
3
4
3
4
2
d
a
L
10
basal plane and the bidentate diphosphine ligand taking two axial
positions. The mean value of the IrAIr distance (2.769(3) ) is
longer than that reported for the [PPN][Ir4(CO)10((Ph2P)2CH)],
while the IrAH distance (2.08(6) ) is longer than those found for
monometallic complexes [24]. The exact location of the hydride
ligand in the complex could not be successfully dened by
conventional X-ray diffraction analysis. Consequently, a neutron
diffraction experiment was performed at the Institute Laue
Langevin in Grenoble [26]. Fig. 4 illustrates the outcome of this
experiment. The IrAH distance found is 1.618(14) and it is the
rst experimental determination of an iridium cluster. Comparison
with the value above reported of 2.08(6) proves the latter to be
incorrect and, conrms the predictive power of ab initio
calculations [26], and, at the same time, highlights once more the
limits of conventional X-ray diffraction analysis in dening the
position of light atoms in the proximity of heavy ones.
As described above, Ir4(CO)10(l-dppm) quickly reacts with an
excess of KOH to give [Ir4(CO)10(l-(PPh2P)2CH)], which in turn converts into the decarbonylated anion [PPN][Ir4(CO)9(l3-(PPh2P)2CH)],
whereas the hydrido-derivative Ir4H(CO)9(l-dppm) is obtained if
the same reaction is carried out with an excess of DBU. Detti and
co-workers [27] further studied this reaction in dichloromethane
with an excess of DBU and PPNCl, using different phosphines
and arsines, such as: bis(diphenylphosphino)methane, 1,1-bis
(diphenylphosphino)ethane, 1,2-bis(diphenylphosphino)ethane, 1,
3-bis(diphenylphosphino)propane and bis(diphenylarsino)methane. All the corresponding hydrido-complexes (12, 13, 14, 15, 16,
respectively) were obtained with more than 75% yield. The
proposed mechanism requires the nucleophilic attack of OH on
the metal carbonyl, as in Scheme 5:
On the contrary, the reaction of Ir4(CO)10(l-dppmMe) carried
out in presence of an excess of DBU, but without PPNCl, the hydrido-compound (13a) (75% yield, see Scheme 6) with [DBUH]+ as
counterion was obtained together with a secondary derivative
(13b, 1%) with [DBUMe]+. Using Ir4(CO)10(L) (L = dppm, dppe, dppp,
dpam) as starting materials and the same reaction conditions used
for Ir4(CO)10(l-dppmMe) does not lead to the formation of the
analogous hydrides-anions. The explanation appears to be that
the nucleophilic attack by such a strong base as DBU on a diphosphinic chain produces a lack of a site and this is related with the
weak acidity of the methyl group [28]. The compounds (1216)
show the characteristic IR bands in the bridging CO region. The
31
P {1H} NMR spectra have only one signal for the diphosphine, like
the starting complexes. The hydrido ligand is located in axial position and presents a single 1H NMR signal at low eld (15 ppm).
Finally, the low-temperature 13C{1H} NMR spectra obtained from
enriched compounds show the typical pattern of carbonyls.
The molecular structures of compounds (13) with counterion
[DBUH]+ and [DBUMe]+ respectively, and (14, 15) with [PPN]+ are
illustrated in Fig. 5. All structures show the diphosphinic and
hydride ligands in axial position with respect to the Ir1AIr2AIr3
plane that also accommodates three bridging CO units.
96
Fig. 4. Left: ORTEP drawing of the [HIr4(CO)9(l-dppm)] (12) obtained from X-rays diffraction. Right: Structure obtained from neutron diffraction.
Ir
H2O -H+
Ir C
CO
OH
Ir
CO2
Ir
Ir
C
-dbuH+
Ir
Ir
H
C
Ir
Ir
CH3
+H+
CH(CH3)
Ir
Ir
75 %
+ dbu
CH3
-dbuCH3+
C
Ir
+H+
CH2
Ir
Scheme 6. The formation of hydride-derivatives with two possible types of direct attack of dbu.
1%
97
Fig. 5. (A,B) Molecular structures of [HIr4(CO)9(dppmMe)] 13a with [DBUH+] and [DBUMe+] 13b as counterion, respectively; (C,D) molecular structures of [HIr4(CO)9(dppe)]
14 and [HIr4(CO)9(dppp)] 15, respectively, both with [PPN]+ as counterion.
17A
18A
d'
a
f *C
c b
L
b'
d'
a
L *C
c b
c'
e'
e'
b'
g
e
17B
18B
18C
b'
*C
a
f c'
c b
L
*C = COCH2CH2O.
98
19A
*C
a c
f
*C a'
*C
*C
a c
f
a'
e'
e'
e'
19C
19B
*C
a'
c
PPh3
PPh3
PPh3
*C
b
f *C
PPh2
20A
Ph2P b
7. Phosphites
g
g
*C
b
b c
f
Ph2P b
PPh2
20B
99
g
e
d
b
f
PPh 2 (O Ph)
d
d
d
c
PPh 2 (OPh)
Table 1
Activation parameters at 298 K; h = Tolmans cone angle [4].
L
h(deg)
DG (kJ mol1)
PPh3
PPh2(OPh)
PPh2(OMe)
P(OMe)3
145
139
132
107
45.6 0.4
44.3 0.8
42.8 0.8
37.5 0.4
tetrahedral Ir4 core with three CO units bridging to the basal face
and with the phosphite ligands in axial and radial positions. The
average IrAIr distance for 27 is 2.724 , a value consistent with
those found for related compounds such as Ir4(CO)10{P(OMe)3}2,
2.728 , and Ir4(CO)10(PPh3)2, 2.739 [33], and also in the IrAIr
distance range of dodecacarbonyl derivatives, but longer than that
of Ir4(CO)12 (2.693 ). The Ir2AIr3 bond (2.702(10) ) (see Fig. 8) is
considerably shorter than Ir2AIr4 (2.7399(7) ) and Ir3AIr4
(2.7419(6) ). Moreover, as observed for Ir4(CO)10(PPh3)2, the distances between the iridium atoms of the basal plan and the one
in apical position (Ir1) are all different: 2.7367(6) (Ir2AIr1),
2.7159(6) (Ir4AIr1) and 2.7089(6) (Ir3AIr1). The IrAP distances
for P4 (radial) and P2 (axial), are 2.262(2) and 2.251(2) , respectively. They are shorter than those found in bis-diphenylphosphino
derivatives [33], because the two AOCH3 groups make the ligand a
good p-accepter.
The metalmetal bond distances in the basal plane (Ir2AIr3;
where the bound phosphorus atoms are located) for 29 are longer
than the other (2.770 versus 2.755 Ir3AIr4, and 2.762 Ir2AIr4),
and the Ir1AIr4 are shorter than the other (2.735 versus 2.7678
Ir1AIr3 and 2.7624 Ir1AIr2).
100
Fig. 8. ORTEP view of the molecular structure of 27 and 29. Thermal ellipsoids at 50% probability.
A
g
c
c
c
S
b
S
b
a
b
without any bridging CO. The CAO bond lengths are in the typical
range for terminal CO groups. Interestingly, complex (30) can exist
in two conformations (A and B). Upon coordination to the axial
positions, the ligand forms a ve-member ring, where C1 may stay
apart from the Ir1AIr2AIr3 plane or lie beneath. Of course, each
one of these conformers may also have two isomers (a and b),
Ir4
Ir2
Ir3
Ir2
Ir3
Ir1
Ir1
X
X
H
CH3
C1
X
H3C
b
Conformers A
CH3
C1
CH3
b
Conformers B
Scheme 11. The two conformation A and B with the two possible isomers a and b (X = SCH3, PCH3).
101
1
DG
.
1 = 42.6 0.4, DG2 = 47.0 0.4 and DG3 = 58.0 0.8 kJ mol
The cluster 31 has the same geometry both in solution and in
the solid state. The 13CO-enriched (30%) 13C{1H} NMR spectrum
of compound 31 shows seven resonances at: 223.5 (a), 203.8 (b),
179.5 (f), 171.3 (d), 163.8 (c), 162.2(e) and 157.7(g) ppm, with
relative intensities 1:2:2:1:1:1:2. The 2D-EXSY spectrum of 31 in
THF at 215 K is similar to that of 32 [18]. The lowest energy
process, again, the merry-go-round one, involves with rate
constant k1 the a, b, f and d CO units. At 247 K, the signal for CO
c starts to broaden (rate constant k2), while at 287 K emerges the
exchange between CO g and e. The free activation enthalpies, calculated by Eyring linear regression equation are: DG
1 = 38.7 0.4,
1
DG
.
2 = 50.4 0.4 and DG3 = 60.1 0.6 kJ mol
The unobserved intermediate of merry-go-round in
complexes 31 and 32 has a geometry with all CO in terminal positions. It may be that the transition state for the merry-go-round
102
1
lower than that calculated for 32 (DG
and
1 = 38.7 kJ mol
1
53.9 kJ mol respectively).
[19]
[20]
References
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