Synthesis and structure of the first monomeric iridium-siloxide complexes

Article abstract of DOI:10.1016/S0020-1693(02)00855-1

The first monomeric iridium-siloxide complexes [Ir(cod)(PCy ₃)(OSiMe₃)] (1), [Ir(cod)(PCy₃)(OSiMe ₂CH=CH₂)] (2) and [Ir(CO)(PPh₃) ₂(OSiMe₃)] (3), whose structures have

Full text of DOI:10.1016/S0020-1693(02)00855-1

Inorganica Chimica Acta 334 (2002) 301Á307
/
www.elsevier.com/locate/ica
Synthesis and structure of the first monomeric iridiumÁ
/
siloxide
complexes
Ireneusz Kownacki, Maciej Kubicki, Bogdan Marciniec *
Department of Organometallic Chemistry, Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan´, Poland
Received 15 October 2001; accepted 25 January 2002
Dedicated to Professor Andy Wojcicki in recognition of his great contribution to coordination chemistry
Abstract
The first monomeric iridiumÁ
/
siloxide complexes [Ir(cod)(PCy3)(OSiMe3)] (1), [Ir(cod)(PCy3)(OSiMe2CHꢀ
/CH2)] (2) and
[Ir(CO)(PPh3)2(OSiMe3)] (3), whose structures have been successfully determined by the X-ray method, have been synthesised
and characterised by 1H, 13C, 31P and 29Si NMR spectroscopy. In all three complexes the coordination of iridium is square planar.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Iridium complexes; Siloxide ligands; Square planar coordination
1. Introduction
[{Rh(diene)(m-OSiMe3)}2], where dieneꢀ
/cod [8a,8b],
nbd [8c].
Molecular complexes incorporating Mꢁ
/
Oꢁ
/
Si bonds
Catalytic activity of the molecular well-defined cata-
lysts has been illustrated in some reactions [10,13,14],
e.g. [{Rh(cod)(m-OSiMe3)}2] in the hydrosilylation of
alkenes [13] and silylative coupling of vinylsilanes with
alkenes [14]. Per analogy to the rhodium analogue, the
(where Mꢀtransition metal) are good models for metal
/
complexes immobilized on silica and/or silicated sur-
faces, which have been commonly used in catalysis [1].
While complexes of early transition elements contain-
ing siloxy ligands are well known and characterised, the
first iridiumÁsiloxide dimeric complex [{Ir(cod)(m-
/
data on the late transition metalÁ
molecular form are scarce [2]. Siloxy derivatives of iron
[3], cobalt [4], nickel [5], ruthenium [6], rhodium [7Á10]
/
siloxide complexes in
OSiMe3)}2] has been recently synthesised and its struc-
ture was successfully determined by the X-ray method
[15]. The complex has a roof-shaped bis-square planar
geometry and appeared to be a selective catalyst of
silylative coupling of styrene with vinyltrisubstituted
/
and platinum [11] and to a minor extent also osmium
[12] and iridium [11c] have been synthesised and
characterised spectroscopically, and the structures of
most of them have been resolved by X-ray studies.
In particular the complexes containing Rhꢁ
bond have been a subject of recent interest. The
complexes included [{Rh(CO)2(m-OSiR3)}2] where Rꢀ
Me [9], Ph [7b] and [{Rh(cod)(m-OSiPh3)}2] [7b],
silanes (CH2ꢀ
vinylation) of styrene with vinyltris(trimethylsiloxy)si-
lane (CH2ꢀCHSi(OSiMe3)3) [15].
/
CHSiR3) and/or co-dimerisation (hydro-
/
Oꢁ
/
Si
/
Vaska analogue of iridium siloxide, i.e. [Ir(CO)(P-
Ph3)2(OSiMe3)] is to our knowledge the only one
monomeric iridium complex containing siloxy ligand
synthesised and characterised spectroscopically by
Schmidbaur and Adlkofer [11c].
/
The aim of this work is to prepare the monomeric
* Corresponding author. Tel.: ꢁ
1508.
E-mail address: marcinb@main.amu.edu.pl (B. Marciniec).
/
48-61-829 1366; fax: ꢁ48-61-829
/
iridiumÁ
/
siloxide complexes and for the first time to
determine their structure by the X-ray method.
0020-1693/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 0 - 1 6 9 3 ( 0 2 ) 0 0 8 5 5 - 1

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I. Kownacki et al. / Inorganica Chimica Acta 334 (2002) 301Á307
/
2. Experimental
contents were subjected to fraction distillation collecting
the fraction in the range 92Á97 8C. The distillate was
placed over the 4 A sieves for 24 h. The product was
/
2.1. General methods and chemicals
obtained with 85% yield.
All syntheses and operations were carried out using
standard Schlenk techniques under a carefully deoxyge-
2.3.2. Preparation of NaOSiMe2CHꢀ
/
CH2
1
nated and dried Ar. H, 13C, 31P and 29Si NMR spectra
Portions of 70 ml of anhydrous and deoxidised THF
and 3.45 g (0.15 mol) of metallic Na were placed into a
double-necked round-bottomed flask of 100 ml in
capacity, equipped with a reflux condenser and an
attachment for gas supply. Then 13 g (0.127 mol) of
were recorded on a Varian Mercury and Varian Gemini
300 VT spectrometers. The reagents were obtained from
the following sources: C6H6 from OBR PR Plock
(Poland), triphenylphosphine from Fluka, sodium tri-
methylsilanolate from Aldrich, chlorodimethylvinylsi-
lane from Wacker Chemie, THF and C5H12 from POCh
Gliwice, (Poland). All solvents were distilled in inert
atmosphere prior to use. [{Ir(cod)(m-Cl2)}2] [16a],
[Ir(Cl)(CO)(PPh3)2] [16b] and [{Ir(cod)(m-OSiMe3)}2]
[15] were prepared according to the previously reported
procedures.
HOSiMe2CHꢀ/CH2 in small portions was introduced
over 45 min. After this time the mixture was heated at a
boiling point for 3 h. After the reaction the contents of
the flask were hot filtered off through a cannula to a
Schlenk’s flask. Having cooled the contents, the solvent
was evaporated and the white solid was dried in vacuum
1
for 7 h. The product was obtained with a 95% yield. H
NMR (ppm, C6D6): d 0.28 (s, 6H, ꢁ
/CH3); 5.90 (qd, 2H,
2.2. Synthesis of the complex
[Ir(cod)(PCy3)(OSiMe3)] (1)
ꢀ
/
CH2); 6.44 (dd, 1H, ꢁCHꢀ).
/
/
2.3.3. Preparation of [Ir(cod)(Cl)(PCy3)]
Portions of 0.3 g [{Ir(cod)(m-OSiMe3)}2] (0.39 mmol)
and 0.22 g (0.79 mmol) PCy3 were placed in a Schlenk
flask in Ar atmosphere. Then 3 ml of dried and
deoxidised C5H12 were added. The reaction was carried
out for 24 h at room temperature (r.t.). After that time
1/3 of the solvent was evaporated and the concentrated
Portions of 0.43 g (1.5 mmol) of PCy3 and 0.5 g (0.75
mmol) of [{Ir(cod)(m-Cl)}2] were placed in a Schlenk’s
flask in Ar atmosphere. Then 6 ml of dried and
deoxidised C6H6 was added and the mixture was stirred
with a magnetic stirrer. After 30 min fine-crystalline
precipitate started to appear. The reaction was contin-
ued for 1 h and then C6H6 was evaporated to 1/3 of the
initial volume and 5 ml of dried and deoxidised C5H12
was added. The precipitate was three times decanted by
C5H12. The complex was dried in vacuum for about 3 h.
solution was left to crystallise for 24 h at ꢂ
/
20 8C. At
35Á30 8C
the next step the contents were cooled to ꢂ
/
/
and this temperature was kept for 1 h. After this time the
liquid was decanted and the precipitate dried over
vacuum. The complex was obtained with a yield of
1
1
It was obtained with a yield of 95%. H NMR (ppm,
70%. H NMR (ppm, C6D6): d 0.46 (s, 9H); 1.14Á
/
2.39
(m, 37H); 3.01 (m, 4H); 5.00 (m, 4H). 13C NMR (ppm,
C6D6): d 86.6, 86.4 (cod, ꢀCHꢁ); 45.05 (cod, ꢁCH2ꢁ);
34.69, 34.65, 32.12, 31.94, 31.82, 30.53, 29.88, 28.32,
28.19, 27.15 (ꢁCy, ꢁCH2ꢁ); 5.9 (ꢁOSi(CH3)3, ꢁCH3).
31P NMR (ppm, C6D6): d 16.6. 29Si NMR (ppm, C6D6):
d ꢂ1.2.
C6D6): d 1.13Á
/
2.2 (m, 33H, ꢁ
/
Cy); 2.35 (m, 4H, ꢁ
/
CH2ꢁ
/
); 3.22 (m, 4H, ꢁ
/
CH2ꢁ
/
); 5.28 (m, 4H, ꢀCHꢁ
/
/
/
/
/
/
cod). 31P NMR (ppm, C6D6): d 14.7.
/
/
/
/
/
2.3.4. Preparation of 2
Portions of 0.5 g (0.81 mmol) [{Ir(cod)(Cl)(PCy3)] and
0.12 g (0.97 mmol) NaOSiMe2CHꢀCH2 were placed in a
/
/
2.3. Synthesis of the complex
[Ir(cod)(PCy3)(OSiMe2CHꢀ
Schlenk flask in Ar atmosphere. Then 4 ml of dried and
deoxidised C6H6 were added. The reaction was con-
ducted for 24 h at r.t. After this time C6H6 was
evaporated and 10 ml of dried and deoxidised C5H12
were added. The entire mixture was filtered of by a
cannula system. From the obtained filtrate the solvent
/
CH2)] (2)
2.3.1. Preparation of HOSiMe2CHꢀ
/
CH2
Portions of 300 ml of distilled water, 12 g (0.16 mol)
HNEt2 and 200 ml Et2O were placed in a double-necked
round-bottomed flask. The contents were cooled to
0 8C. To this mixture a portion of 18 g (0.15 mol) of
was evaporated leaving yellowÁ
plex was obtained with a yield of 90%. H NMR (ppm,
C6D6): d 0.31 (s, 6H, ꢁCH3); 1.15Á2.18 (m, 33H, Cy);
2.3 (m, 4H, ꢁCH2ꢁ); 3.05 (m, 4H, cod); 5.05 (m, 4H,
cod); 6.05 (qd, 2H, ꢀCH2); 6.70 (dd, 1H, ꢁCHꢀ
). 13C
NMR (ppm, C6D6): d 145.58, 130.76 (ꢁCHꢀCH2);
87.00, 86.80 (cod, ꢁCHꢀ); 45.24 (cod, ꢁCH2ꢁ); 34.68,
34.65, 32.13, 31.83, 30.74, 30.54, 29.81, 28.32, 28.18,
27.15 (ꢁCy, ꢁCH2ꢁ); 3.58 (ꢁCH3, ꢁOSi(CH3)2CHꢀ
/
orange solid. The com-
1
CH2ꢀ/CHSiMe2Cl was added in the time of 30 min on
/
/
constant stirring by a magnetic stirrer. The process of
hydrolysis was conducted for 2 h until the conversion of
the initial chlorosilane was complete. After the reaction
completion the ether layer was separated and placed
over anhydrous CaCl2. After 5 h the mixture was
decanted and ether was evaporated. The remaining
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/

I. Kownacki et al. / Inorganica Chimica Acta 334 (2002) 301Á
/307
303
CH2). 31P NMR (ppm, C6D6): d 16.6 (PCy3). 29Si NMR
(ppm, C6D6): d ꢂ10.41.
2.5. X-ray crystallography
Single crystals of the complexes 1Á
/
/
3 were grown by
slow evaporation from the solution. Diffraction data
from pale-yellow plate-shaped crystals, sealed in a glass
capillary, were collected on a KUMA KM4CCD
2.4. Preparation of the complex
[Ir(CO)(PPh3)2(OSiMe3)] (3)
diffractometer [17] at r.t., using graphite-monochro-
˚
Portions of 0.5 g (0.64 mmol) of [Ir(Cl)(CO)(PPh3)2]
and 0.08 g (0.71 mmol) of NaOSiMe3 were placed in a
Schlenck flask in Ar atmosphere. Then an amount of 4
ml of dried and deoxidised C6H6 was added. The
reaction was conducted for 5 h at 60 8C on intense
stirring with a magnetic stirrer. After the reaction
completion, C6H6 was evaporated and the Schlenck
flask content was supplemented with 3 ml of dried and
deoxidised CH2Cl2. The suspension was filtered off and
the filtrate was concentrated. The bright-yellow preci-
pitate obtained after addition of C5H12 was decanted
with three portions of C5H12 and dried under vacuum.
The siloxyl complex was obtained with a yield of 96%.
mated Mo Ka radiation (lꢀ
/0.71073 A). In each case,
the data collection was performed in six separate runs
(782 frames) in order to cover the symmetry-indepen-
dent part of the reciprocal space. The v-scan was used
with the step of 0.758, two reference frames were
measured after every 50 frames, and they did not show
any systematical changes neither in the peak positions
nor in their intensities. The unit-cell parameters were
determined by the least-squares treatment of the setting
angles of 1420 (1), 2049 (2), and 7220 (3) highest-
intensity reflections, chosen from the whole experiment.
The Lp corrections were applied [18], and then the
intensities were merged and corrected for absorption
with Sortav [19]. The structures were solved by direct
methods with SHELXS-97 program [20], and refined with
the full-matrix least-squares technique by SHELXL-97
[21]. Non-hydrogen atoms were refined anisotropically,
the positions of hydrogen atoms were generated geome-
trically and they were refined as a ‘riding model’ with
1H NMR (ppm, C6D6): d ꢂ
/
0.44 (s, 9H, ꢁ
/
CH3); 7.10 (m,
18H, o,p-Ph); 7.95 (m, 12H, m-Ph). 31P NMR (ppm,
C6D6): d 23.1. 29Si NMR (INEPT) (ppm, C6D6): d
ꢂ
/
6.27 (ꢁ
/
OSiMe3). Complexes 1Á3 are moderate air-
/
sensitive in the solid state, but in the solution, in
the presence of air and moisture, they decompose very
fast.
Table 1
Crystal data, data collection and structure refinement
Compound
1
2
3
Empirical formula
Formula weight
Crystal system
Space group
C29H54IrOPSi
667.97
triclinic
C30H54IrOPSi
681.99
triclinic
C40H39IrO2P2Si×1/2CH2Cl2
876.41
orthorhombic
Pbca
/
P1/
/
P1/
˚
a (A)
10.392(2)
10.518(20)
14.986(3)
104.00(2)
106.04(2)
94.66(2)
1508.1(5)
2
10.386(2)
10.734(2)
17.007(3)
93.37(3)
103.37(3)
110.87(3)
1702.7(5)
2
21.2931(11)
17.1270(9)
22.0303(11)
90
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
90
90
3
˚
V (A )
Z
8034.2(7)
8
1.45
Dx (g cmꢂ3
)
1.47
4.54
1.330
4.021
m (mmꢂ1
F(000)
Crystal size (mm)
)
3.53
3496
680
0.5ꢃ0.2ꢃ0.1
696
0.3ꢃ0.15ꢃ0.1
0.3ꢃ0.2ꢃ0.2
U range (8)
hkl range
3.8Á
/
21
3.7Á
/
25
1.5Á25
/
ꢂ95h 510, ꢂ105k 510,
ꢂ145l 515
7163
ꢂ115h 512, ꢂ125k 58,
ꢂ205l 520
12 640
ꢂ255h 525, ꢂ205k 520,
ꢂ265l 526
58 330
Reflections collected
Reflections unique
3201(0.099)
5930(0.093)
6999(0.088)
(Rint
)
Reflections observed
Parameters
2998
298
2607
298
4253
443
R(F) (observed)
wR(F2)
Goodness-of-fit
0.062
0.144
1.26
0.054
0.088
1.12
0.043
0.096
1.19
ꢂ3
˚
Max./min. Dr (e A
)
2.17/ꢂ2.09
0.88/ꢂ0.62
2.08/ꢂ1.04

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I. Kownacki et al. / Inorganica Chimica Acta 334 (2002) 301Á307
/
[IrCl(CO)(PPh3)2]ꢁNaOSiMe3
C06H12 [Ir(CO)(PPh3)2(OSiMe3)]ꢁNaCl
their Uiso parameters set at 1.2 times Ueq of the
appropriate carrier atom.
A summary of crystal data, data collection and
refinement is given in Table 1.
ꢀ
(3)
60 ꢁC
5 h
(3)
All the iridiumÁsiloxide products were characterised by
/
1H, 13C, 31P and 29Si NMR spectroscopy. The respective
spectra for 1 are enclosed (Fig. 1).
1
The H NMR spectrum of the complex [Ir(cod)(P-
3. Results and discussion
Cy3)(OSiMe3)] (1) (Fig. 1) reveals three groups of signals
from the cyclooctadiene ligand: a multiplet at 5.00 ppm
assigned to equivalent olefin protons and two multiplets
at 3.01 and 2.3 ppm assigned to inequivalent protons at
the alkyl positions. The group of multiplets in the range
Two types of the reactions were used effectively for
the synthesis of the corresponding iridiumÁ
/siloxide
complexes 1Á
/
3
[fIr(cod)(m-OSiMe3)g2]ꢁ2PCy3
C06H12 2[Ir(cod)(PCy3)(OSiMe3)]
1.14Á2.22 ppm is assigned to the protons from the
/
cyclohexyl rings and the singlet at 0.46 ppm corresponds
to the protons from the siloxyl ligand. The 13C NMR
spectrum reveals two close resonance lines assigned to
the olefin carbon atoms, at 86.59 and 86.40 ppm, and
two resonance lines assigned to the alkyl carbon atoms,
at 34.69 and 34.65 ppm. The line at 5.90 ppm
corresponds to the carbon atoms of the methyl groups
of the trimethylsiloxy ligand. The other lines in this
ꢀ
(1)
r:t:; 24
h
(1)
[Ir(cod)(Cl)(PCy3)]ꢁNaOSiMe2CHꢀCH2
C06H12 [Ir(cod)(PCy3)(OSiMe2CHꢀCH2)]
ꢀ
(2)
r:t:; 24
h
(2)
Fig. 1. NMR spectra of the compound 1.

I. Kownacki et al. / Inorganica Chimica Acta 334 (2002) 301Á
/307
305
spectrum are attributed to the carbon atoms of the
cyclohexyl rings attached to the phosphorus atom. The
spectra 31P and 29Si NMR show singlets at 16.6 ppm
The molecular structures of complexes 1Á
atom numbering scheme are depicted in Figs. 2Á4,
respectively. Selected bond distances and angles are
listed in Table 2.
In all three complexes the coordination of iridium is
square planar (in 1 and 2 the middlepoints of double
bonds from cyclooctadiene fragments are regarded as
the coordination sites). This is evident from the inspec-
tion of bond angles as well as from the least-square
plane calculations: the iridium atom deviates from the
plane defined by four coordination sites by 0.011(7),
/
3 with the
/
assigned to 31P and at ꢂ
replacement of (ꢁOSiMe3) by the ligand (ꢁ
CH2) did not disturb significantly the geometry of a
newly formed complex of [Ir(cod)(PCy3)(OSiMe2CHꢀ
/
l.2 ppm assigned to 29Si. A
/
/
OSiMe2CHꢀ
/
/
CH2)], so did not produce significant changes in the
spectroscopic characterisation relative to that of the
complex of [Ir(cod)(PCy3)(OSiMe3)]. For instance in the
31P NMR spectrum, the resonance line is exactly at the
same chemical shift position 16.60 ppm, for the two
complexes. Noticeable changes appear only in the
˚
0.021(3), and 0.020(2) A in 1, 2 and 3, respectively.
The bond lengths are well within the typical range (the
values in parentheses are: mean value from the March
2001 release of CSD [22], number of structures, number
1
chemical shifts of the olefin proton signals in the H
NMR spectrum at 5.05 ppm and in the 13C NMR
spectrum at 87.00, 86.80 ppm. The attachment of a
substituent with electron density of p-symmetry to the
silicon atom had a significant effect on the chemical
shifts of particular nuclei of the vinyldimethylsiloxy
of fragments): Irꢁ
2214), IrꢁC (cod): 2.15(4) (2.17(5), 136, 175), Irꢁ
(PPh3): 2.325(5) (2.34(5), 330, 598), IrꢁP (PCh3):
2.335(5) (2.34(5), 19, 26). Interestingly, in CSD there
are no compounds with the IrꢁOꢁSi fragment. In all
/
C (carbonyl): 1.818(7) (1.87(6), 692,
/
/P
/
/
/
ligand: 1H (0.31 ppm); 13C (3.58 ppm); 29Si (ꢂ
10.41
/
ppm). In the 1H NMR spectrum of the complex
[Ir(CO)(PPh3)2(OSiMe3)] the singlet assigned to the
trimethylsiloxy group appears at ꢂ
/
0.44 ppm. A con-
siderable difference in the chemical shift of the ligand ꢁ
/
OSiMe3 of 0.9 ppm relative to the position in the
spectrum of the complex [Ir(cod)(PCy3)(OSiMe3)] can
be interpreted as a result of the presence of two
triphenylphosphine ligands and trans-effect of carbonyl
group in the coordination sphere of former complex. As
the electron density on iridium atom increases, it is also
increased on the silicon atom leading to a shift of the
resonance lines assigned to the methyl protons towards
higher field. This interpretation is confirmed in the 29Si
NMR spectrum in which the resonance line appears at
ꢂ6.27 ppm.
/
Fig. 3. Molecular structure of complex 2 with 50% probability
ellipsoids. Hydrogen atoms are drawn as spheres of arbitrary radii,
for clarity the labelling of cyclohexyl rings are omitted.
Fig. 2. Molecular structure of complex 1 with 50% probability
ellipsoids. Hydrogen atoms are drawn as spheres of arbitrary radii,
for clarity the labelling of cyclohexyl rings are omitted.
Fig. 4. Molecular structure of complex 3 with 50% probability
ellipsoids. Hydrogen atoms are drawn as spheres of arbitrary radii.

306
I. Kownacki et al. / Inorganica Chimica Acta 334 (2002) 301Á
/307
Table 2
˚
Selected bond lengths (A) and angles (8) with e.s.d.’s in parentheses
Compound 1
Compound 2
Compound 3
Bond lengths
Ir(1)ꢁX(2)
Ir(1)ꢁX(1)
P(1)ꢁC(31)
P(1)ꢁC(21)
Ir(1)ꢁO(51)
Ir(1)ꢁP(1)
1.9779(7)
2.0655(6)
1.853(13)
1.873(13)
2.015(9)
Ir(1)ꢁX(2)
Ir(1)ꢁX(1)
P(1)ꢁC(11)
P(1)ꢁC(31)
Ir(1)ꢁO(5)
Ir(1)ꢁP(1)
P(1)ꢁC(21)
O(5)ꢁSi(5)
2.009(12)
2.099(13)
1.815(14)
1.864(12)
2.003(8)
2.333(4)
1.853(14)
1.595(8)
Ir(1)ꢁC(1)
Ir(1)ꢁP(1)
1.818(7)
2.321(2)
1.153(7)
1.822(6)
1.823(6)
1.840(6)
2.019(4)
2.330(2)
1.592(4)
1.839(6)
1.814(6)
1.830(6)
C(1)ꢁO(1)
P(1)ꢁC(111)
P(1)ꢁC(121)
P(1)ꢁC(131)
Ir(1)ꢁO(2)
Ir(1)ꢁP(2)
O(2)ꢁSi(2)
P(2)ꢁC(211)
P(2)ꢁC(221)
P(2)ꢁC(231)
2.341(3)
1.867(12)
1.600(10)
P(1)ꢁC(11)
O(51)ꢁSi(5)
Bond angles
X(2)ꢁIr(1)ꢁO(51)
O(51)ꢁIr(1)ꢁX(1)
O(51)ꢁIr(1)ꢁP(1)
Si(5)ꢁO(51)ꢁIr(1)
X(2)ꢁIr(1)ꢁX(1)
X(2)ꢁIr(1)ꢁP(1)
X(1)ꢁIr(1)ꢁP(1)
175.6(3)
91.7(3)
86.3(3)
X(2)ꢁIr(1)ꢁO(5)
O(5)ꢁIr(1)ꢁX(1)
O(5)ꢁIr(1)ꢁP(1)
Si(5)ꢁO(5)ꢁIr(1)
X(2)ꢁIr(1)ꢁX(1)
X(2)ꢁIr(1)ꢁP(1)
X(1)ꢁIr(1)ꢁP(1)
176.1(5)
90.9(5)
86.7(3)
154.8(6)
85.5(6)
96.9(4)
177.6(4)
C(1)ꢁIr(1)ꢁO(2)
O(2)ꢁIr(1)ꢁP(1)
O(2)ꢁIr(1)ꢁP(2)
O(1)ꢁC(1)ꢁIr(1)
C(1)ꢁIr(1)ꢁP(1)
C(1)ꢁIr(1)ꢁP(2)
P(1)ꢁIr(1)ꢁP(2)
Si(2)ꢁO(2)ꢁIr(1)
178.7(2)
89.3(1)
91.1(1)
153.0(6)
86.20(3)
95.97(9)
177.50(8)
178.7(6)
89.6(2)
90.0(2)
178.49(6)
156.0(3)
DꢁHꢂ ꢂ ꢂA
d(DꢁH)
d(Hꢂ ꢂ ꢂA)
d(Dꢂ ꢂ ꢂA)
ꢂ(DHA)
C(112)ꢁH(112)ꢂ ꢂ ꢂO(2)
C(232)ꢁH(232)ꢂ ꢂ ꢂO(2)
C(216)ꢁH(216)ꢂ ꢂ ꢂCl(1S)i
C(225)ꢁH(225)ꢂ ꢂ ꢂCl(2S)ii
0.93
0.93
0.93
0.93
2.48
2.55
3.06
2.97
3.262(8)
3.340(8)
3.982(9)
3.76(1)
142.0
143.2
171.5
143.4
X1 and X2 denote the middlepoints of C41ꢁC42 and C45ꢁC46 bonds, respectively (these points are regarded as the coordination sites). Symmetry
transformations used to generate equivalent atoms: i: ꢂx, yꢁ1/2, ꢂzꢁ1/2; ii: ꢂx, ꢂyꢁ1, ꢂz.
three complexes described here, the geometry of these
fragments is similar (cf. Table 2).
molecule is partially stabilised by very weak (but
directional) Cꢁ
/
Hꢂ ꢂ ꢂCl hydrogen bonds. The geometries
of the above-mentioned hydrogen bonds are listed in
Table 2.
In 1 and 2 all cyclohexyl rings adopt almost ideal
chair conformation (the maximum value of asymmetry
parameter [23] equal to ca. 68). The cyclooctadiene
eight-membered rings adopt the lowest-energy C2 twist-
boat conformation [24,25]; the values of asymmetry
parameter C2 are also small: 1.68 for 1 and 3.08 for 2.
Complex 3 has an approximate plane of symmetry
that is determined by the positions of the C1, Ir1 and O2
atoms. The six phenyl rings are almost planar (max-
imum deviation from the least-square planes is 0.021(6)
4. Supplementary material
Additional crystallographic data have been deposited
with the Cambridge Crystallographic Data Centre,
CCDC Nos. 171236, 171237 and 171238 for compounds
1, 2 and 3, respectively. Copies of this information may
be obtained free of charge from The Director, CCDC,
˚
A). The geometry of this complex can be described by
the angles between the normal to the phenyl rings planes
12 Union Road, Cambridge, CB2 1EZ, UK (fax: ꢁ44-
/
and the Cꢁ
/
Irꢁ/O line. These values can be grouped into
1223-336-033; e-mail: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk).
pairs, due to the above-mentioned approximate symme-
try (hereinafter we will identify the rings by the first
atom): C111: 48.3 and C231: 45.38; C121: 71.6 and
C211: 74.2; C131: 29.1 and C221: 14.88. The conforma-
tion of this complex is additionally stiffened by the weak
Acknowledgements
Cꢁ
/
Hꢂ ꢂ ꢂO hydrogen bonds. In the crystal structure there
are empty spaces large enough to accommodate dichlor-
omethane molecule of the solvent (best results were
obtained with the half occupancy of this molecule). This
This work was supported by Grant No K012/T09/
2000 from the State Committee for Scientific Research
(Poland).

I. Kownacki et al. / Inorganica Chimica Acta 334 (2002) 301Á
/307
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