Synthesis of a novel organoiridium(I) fluoro complex

Article abstract of DOI:10.1002/ejic.200400030

Cyclooctadienefluorotriphenylphosphaneiridium(I) [IrF-(C₈H ₁₂)(PPh₃)] (3) was prepared and its structure determined by single crystal X-ray diffraction analysis. Complex 3 crystallises in the monoclinic space group P2₁/n. The lattice parameters are a = 931.9(3) pm, b = 1629.4(7) pm, c = 1592.9(7) pm, α = γ = 90°, β = 92.85(3)°. Number of molecules per unit cell is 4. The square planar iridium complex 3 exhibits an Ir-F bond length of 201.3(5) pm. 3 was obtained in Teflon tubes, whereas the use of glass vessels led to cyclooctadiene- bis(triphenylphosphane)iridium(I)-pentafluorosilicate(IV) ([Ir(C ₈H₁₂)(PPh₃)₂][SiF₅]) (4). The composition of 4 was confirmed by single crystal X-ray diffraction analysis. 4 crystallises in the monoclinic space group P2₁/c. The lattice parameters are a = 1157.4(9) pm, b = 1864.4(9) pm, c = 1922.5(17) pm, α = γ = 90°, β = 96.16(7)°. The number of molecules per unit cell is 4. The square-planar coordinated iridium cation [Ir(C ₈H₁₂)(PPh₃)₂]⁺ is separated from the trigonal bipyramidal [SiF₅]^- anion by 461.1 pm (shortest Ir...F distance) and thus it is assumed that no interactions occur between the fluorine and iridium atoms. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200400030

FULL PAPER
Synthesis of a Novel Organoiridium( ) Fluoro Complex
I
Michael Gorol,[a] Nadia C. Mösch-Zanetti,[a] Herbert W. Roesky,*[a] Mathias Noltemeyer,[a]
and Hans-Georg Schmidt[a]
Dedicated to G.-V. Röschenthaler on the occasion of his 60th birthday
Keywords: Syntheses / Crystal structures / Iridium() / Fluoro complexes / Pentafluorosilicates
Cyclooctadienefluorotriphenylphosphaneiridium(
(C8H12)(PPh3)] (3) was prepared and its structure determined
I
)
[IrF-
firmed by single crystal X-ray diffraction analysis. 4 crys-
tallises in the monoclinic space group P21/c. The lattice para-
by single crystal X-ray diffraction analysis. Complex 3 crys- meters are a = 1157.4(9) pm, b = 1864.4(9) pm, c = 1922.5(17)
tallises in the monoclinic space group P21/n. The lattice para- pm, α = γ = 90°, β = 96.16(7)°. The number of molecules per
meters are a = 931.9(3) pm, b = 1629.4(7) pm, c = 1592.9(7)
unit cell is 4. The square-planar coordinated iridium cation
pm, α = γ = 90°, β = 92.85(3)°. Number of molecules per unit
[Ir(C8H12)(PPh3)2]+ is separated from the trigonal bipyramidal
cell is 4. The square planar iridium complex 3 exhibits an [SiF5]− anion by 461.1 pm (shortest Ir···F distance) and thus it
Ir−F bond length of 201.3(5) pm. 3 was obtained in Teflon
tubes, whereas the use of glass vessels led to cyclooctadiene-
is assumed that no interactions occur between the fluorine
and iridium atoms.
bis(triphenylphosphane)iridium(
([Ir(C8H12)(PPh3)2][SiF5]) (4). The composition of 4 was con-
I
)-pentafluorosilicate(IV)
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
Moreover, complexes of weakly or non-coordinating flu-
orinated anions such as [BF4]Ϫ, [PF6]Ϫ, [AsF6]Ϫ and
[SbF6]Ϫ are of special interest in organometallic fluorine
There is ongoing interest in low oxidation state transition
metal compounds containing fluorine-metal and carbon-
metal bonds as a result of their use in synthesis and
catalysis.[1Ϫ3] In the presence of π back-bonding ligands
fluoro complexes of d8 metals are stable although they object
the predicted hard/soft acid/base (HSAB) rules. This has
been shown for the iridium Vaska system IrF(CO)(PPh3)2,
whose derivatives are the only known organometallic fluor-
ides in the chemistry of iridium().[1,4] Compounds of this
type are certainly the most extensively studied and readily
prepared systems but structural characterisation has not
been accomplished. Thus far, bond length parameters are
available only for iridium d6 centers e.g. Cp*
chemistry.
For
instance,
the
iridium
complex
[Ir(C8H12)(PCy3)(py)][PF6] has been widely used as a cata-
lyst for the reduction of hindered alkenes and
[Ir(C8H12)(PPh3)2][PF6] has also proven to be useful as a
hydrogenation catalyst.[13,14] However, the investigation of
pentacoordinate fluorosilicon anions enjoys increasing
interest. Large cations are required for the stabilisation of
the rather unstable [SiF5]Ϫ anion ([SiF5]Ϫ Ǟ SiF4 ϩ FϪ).[15]
In recent years a rising number of transition metal com-
plexes containing [SiF5]Ϫ, like in [PtCl(CO)(PEt3)2]-
[SiF5],[16] [Ir(H)2(CO)(PPh3)3][SiF5],[17] [Au(PPh3)3][SiF5],[18]
[Ir(CO)2(PtBu2Ph)2][SiF5],[19]
[Ir(H)2(CO)2(PtBu2Ph)2]-
[SiF5][19] and [Co(NioxH)2(PPh3)2][SiF5] (NioxH2 is 1,2-
IrF(Ph)(PMe3),[5]
Ir(Cl)F(NSF2)(CO)(PPh3)2,[6]
[IrF-
cyclohexanedione dioxime)[20] have been reported.
(η2-NHϭNC6H3-2-CF3)(CO)(PPh3)2][BF4],[7] Ir(FBF3)Me2-
(PMe2Ph)3,[8] and [Ir{C(F)O}F(CO)2(PEt3)2][BF4].[9] Irid-
ium() complexes with cyclooctadiene or cyclooctene as the
stabilising C-based ligands are well-known and widely used
as starting materials in organometallic chemistry. However,
appropriate fluorides are missing, although some are ac-
cessible, as in the case of homologous rhodium() olefin
complexes.[10Ϫ12]
Herein, we describe the syntheses and characterisations
of
the
novel
organoiridium()
fluoro
complex
IrF(C8H12)(PPh3) (3) and of the complex salt
[Ir(C8H12)(PPh3)2][SiF5] (4). The crystal structure analysis
of 3 lead to the first iridium() fluorine bond parameters,
whereas that of 4 is probative for the formation of the
[SiF5]Ϫ anion.
Results and Discussion
[a]
Institut für Anorganische Chemie der Universität Göttingen,
Tammannstr. 4, 37077 Göttingen, Germany
Fax: (internat.) ϩ49-(0)551-393373
E-mail: hroesky@gwdg.de
During our research with the aim of obtaining novel irid-
ium fluorides, the use of most of the usual fluorination ag-
2678
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejic.200400030
Eur. J. Inorg. Chem. 2004, 2678Ϫ2682

Synthesis of a Novel Organoiridium(I) Fluoro Complex
FULL PAPER
Scheme 1
ents including AgF, Me3SnF, (Me2N)3Sϩ(Me3SiF2)Ϫ (TAS- are longer than the Ir(1)ϪC(1) and Ir(1)ϪC(2) ones (Fig-
F) or XeF2 failed. The synthesis of IrF(C8H12)(PPh3) (3) ure 1). The Ir(1)ϪF(1) bond length of 201.3(5) pm in 3 is
was finally successful using aqueous HF as the fluorinating shorter than those in iridium d6 compounds, e.g. Cp*
agent, according to the procedure described for the rho- IrF(Ph)(PMe3) 206.9(4) pm,[5] Ir(Cl)F(NSF2)(CO)(PPh3)2
dium() analogue.[10]
208.9(4),[6] [IrF(η2-NHϭNC6H3-2-CF3)(CO)(PPh3)2][BF4]
Treatment of a solution of [Ir(µ-OH)(C8H12)]2 (1)[21] in 221(4) pm,[7] and Ir(FBF3)Me2(PMe2Ph)3 238.9(7) pm.[8]
THF with 73% aqueous HF in a Teflon tube gave com- This might be due to π back-donation of the olefin ligand
pound 2 as a yellow precipitate in virtually quantitative in 3, causing stabilisation of such complexes.[4] The only
yield (Scheme 1). Due to its insolubility in organic solvents exception
is
the
iridium()
fluoro
complex
NMR spectroscopic data are not available and, unfortu- [Ir{C(F)O}F(CO)2(PEt3)2][BF4] with an IrϪF separation of
nately, the mass spectrum only shows the fragmentation 199.8(3) pm.[9] Complex 3 represents the first crystal struc-
pattern of the coordinated cyclooctadiene ligand. The for- ture to be determined for an organoiridium() fluoro com-
mation of an iridium fluoro complex can only be derived plex.
from the IR spectrum of compound 2, which exhibits the
ν˜IrF stretching mode at 478 cmϪ1 similar to that of ν˜IrF
ϭ
451 cmϪ1 in IrF(CO)(PPh3)2.[22] Therefore, a polymeric
structure for compound 2 is proposed.
Reaction of triphenylphosphane with a suspension of 2
in THF results in the formation of a reddish solution. After
addition of pentane, IrF(C8H12)(PPh3) (3) crystallised as an
1
orange solid. The H NMR spectrum of 3 shows two sets
of resonances for the four olefinic protons of the cyclooc-
tadiene ligand. Due to the asymmetric coordination at the
iridium() centre, one resonance appears at δ ϭ 5.42 ppm
(m, 2 H), whereas the other one is shifted upfield to δ ϭ
2.59 ppm (m, 2 H). These values are similar to those (δ ϭ
5.15 and 2.73 ppm) reported for IrCl(C8H12)(PPh3).[23] The
difference between the two signals is presumably due to the
Figure 1. Molecular structure of IrF(C8H12)(PPh3) (3) (without
THF) with 50% probability ellipsoids and the labelling scheme;
selected bond lengths (pm) and angles (°): Ir(1)ϪF(1) 201.3(5),
Ir(1)ϪC(1) 209.3(9), Ir(1)ϪC(2) 208.7(8), Ir(1)ϪC(5) 218.9(8),
unequal trans influence of PPh3 and FϪ. In the 19F NMR Ir(1)ϪC(6) 217.2(7), C(1)ϪC(2) 140.0(13), C(5)ϪC(6) 139.3(12),
Ir(1)ϪP(1) 231.93(19), P(1)ϪC(11) 181.9(7), P(1)ϪC(21) 181.7(7),
P(1)ϪC(31) 181.8(8); F(1)ϪIr(1)ϪC(1) 161.2(3), F(1)ϪIr(1)ϪC(2)
157.9(3), F(1)ϪIr(1)ϪC(5) 88.6(3), F(1)ϪIr(1)ϪC(6) 86.6(3),
F(1)ϪIr(1)ϪP(1) 90.32(15), C(1)ϪIr(1)ϪP(1) 97.8(2), C(2)ϪIr(1)Ϫ
P(1) 92.3(2), C(5)ϪIr(1)ϪP(1) 159.0(2), C(6)ϪIr(1)ϪP(1) 163.5(2)
spectrum of 3, a singlet was observed at δ ϭ Ϫ219.3 ppm,
characteristic of an iridium()-bound fluorine atom and the
31P{1H} NMR spectrum displays a singlet at δ ϭ 25.1 ppm.
Single crystals suitable for X-ray diffraction analysis of 3
were obtained by slow diffusion of pentane into a concen-
trated THF solution. Compound 3 crystallises in the mono-
However, treatment of 1 with aqueous HF carried out in
clinic space group P21/n. The asymmetric unit contains one glass vessels resulted in deep red crystals. This side product
molecule of IrF(C8H12)(PPh3) and half a solvent molecule is insoluble in THF, but can be recrystallised from a di-
of THF. Figure 1 shows the molecular structure of chloromethane/pentane mixture. This compound was un-
IrF(C8H12)(PPh3) (3) along with selected bond lengths and ambiguously
identified
as
the
complex
salt
angles. As expected from the larger trans influence of PPh3 [Ir(C8H12)(PPh3)2][SiF5] (4) by IR and NMR spectroscopy
with respect to FϪ, the Ir(1)ϪC(5) and Ir(1)ϪC(6) distances as well as single crystal structure analyses. The formation
Eur. J. Inorg. Chem. 2004, 2678Ϫ2682
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2679

M. Gorol, N. C. Mösch-Zanetti, H. W. Roesky, M. Noltemeyer, H.-G. Schmidt
FULL PAPER
of the cationic iridium complex [Ir(C8H12)(PPh3)2]ϩ in the
presence of weakly coordinating anions is well-known.[14]
In addition, the appearance of the [SiF5]Ϫ anion is not un-
expected, if reactions involving HF are carried out in glass
vessels.[20] Thus, the reaction of 1 in THF with an excess of
aqueous HF in a glass vessel affords 4 in quantitative yield,
after two equiv. of triphenylphosphane were added
(Scheme 1). The 1H NMR spectrum of 4 shows three reson-
ances of equal intensity for the protons of the cyclooc-
tadiene ligand [δ ϭ 4.20 (br. s, 4 H), δ ϭ 2.33 (m, 4 H) and
δ ϭ 1.97 ppm (m, 4 H)]. These values are similar to δ ϭ
4.14 (s, 4 H) and δ ϭ 2.12 ppm (m, 8 H) found in
[Ir(C8H12)(PPh3)2][BF4].[24] The formation of the cationic
bisphosphane complex is best documented by its 13C NMR
spectrum. The resonance for the carbon atoms of the
ϭCHϪ groups of the cyclooctadiene ligand appears as a
triplet [δ ϭ 87.40 ppm (t, J ϭ 5.58 Hz)] indicative of coup-
ling to two phosphorus nuclei, whereas the ϪCH2Ϫ groups
show a singlet at δ ϭ 31.37 ppm. In the 19F NMR spectrum
a broad resonance (δ ϭ Ϫ139.1 ppm) is observed. This is
in good agreement with that reported (δ ϭ Ϫ139 ppm) for
the [SiF5]Ϫ anion in [Au(PPh3)3][SiF5].[18] The 31P NMR
resonance is shifted upfield in comparison to that of com-
pound 3 and appears as a singlet at δ ϭ 17.4 ppm. Com-
Figure 2. Molecular structure of the [Ir(C8H12)(PPh3)2]ϩ cation in
4 with 50% probability ellipsoids and the labelling scheme; selected
bond lengths (pm) and angles (°): Ir(1)ϪC(1) 221.5(11), Ir(1)ϪC(2)
223.5(10), Ir(1)ϪC(5) 216.5(11), Ir(1)ϪC(6) 219.5(11), Ir(1)ϪP(1)
233.1(3), Ir(1)ϪP(2) 235.3(3), C(1)ϪC(2) 140.8(16), C(5)ϪC(6)
132.3(19), P(1)ϪC(11) 184.1(11), P(1)ϪC(21) 180.6(11),
P(1)ϪC(31) 181.4(10), P(2)ϪC(41) 183.0(11), P(2)ϪC(51)
184.3(10), P(2)ϪC(61) 183.9(11); C(1)ϪIr(1)ϪP(1) 153.7(3),
C(2)ϪIr(1)ϪP(1) 168.7(3), C(5)ϪIr(1)ϪP(1) 95.6(3), C(6)ϪIr(1)Ϫ
P(1) 89.5(3), C(1)ϪIr(1)ϪP(2) 93.9(3), C(2)ϪIr(1)ϪP(2) 86.7(2),
˜
pound 4 gives rise to bands in the infrared spectrum at (ν ϭ
879, 790, 479 and 448 cmϪ1 CsI plates), due to SiϪF modes
similar to those reported in the literature.[16]
C(5)ϪIr(1)ϪP(2)
152.0(4),
C(6)ϪIr(1)ϪP(2)
170.4(4),
Single crystals suitable for X-ray diffraction analyses of
4 were obtained by slow diffusion of pentane into a concen-
trated CH2Cl2 solution. Compound 4 crystallises in the
monoclinic space group P21/c. A structure determination
showed one [Ir(C8H12)(PPh3)2]ϩ cation, one non-coordi-
nated [SiF5]Ϫ anion and a solvent molecule CH2Cl2 in the
asymmetric unit. The cation is depicted in Figure 2 together
with selected bond lengths and angles. The iridium-phos-
phorus bond lengths [Ir(1)ϪP(1) 233.1(3) and Ir(1)ϪP(2)
235.3(3) pm] are similar to those of IrϪP(1) 236.7(2) and
IrϪP(2) 232.6(3) pm found in [Ir(C8H12)(PPh3)2][PF6].[14]
The [SiF5]Ϫ anion is not coordinated to an iridium atom
(shortest Ir···F distance is 461.1 pm). The geometry of the
silicon atom is regular bipyramidal. The SiϪFeq bond
lengths are Si(1)ϪF(1) 158.4(10), Si(1)ϪF(3) 159.8(10) and
Si(1)ϪF(5) 158.3(10) pm. The SiϪFax distances are longer,
with values of Si(1)ϪF(2) 162.3(10) and Si(1)ϪF(4)
162.5(11) pm. The bond lengths and angles for the [SiF5]Ϫ
anions in the compounds [Au(PPh3)3][SiF5], [Ir(CO)2-
(PtBu2Ph)2][SiF5] and [Ir(H)2(CO)2(PtBu2Ph)2][SiF5], are in
the same range as those for compound 4.[18,19]
P(1)ϪIr(1)ϪP(2) 94.43(9)
tributable to a ν˜CO mode. These data lead to the assumption
that one of the products of the decomposition of 3 is the
Vaska complex IrF(CO)(PPh3)2. The formation of a car-
bonyl complex is in agreement with reports of the ability
of rhodium() systems to abstract carbon monoxide from
oxygen-containing organic solvents.[25]
Conclusion
The present study describes the synthesis and characteris-
ation of IrF(C8H12)(PPh3) and provides the first crystallo-
graphic data for an organoiridium() fluoro complex. The
reaction of [Ir(µ-OH)(C8H12)]2 with concentrated aqueous
HF yields the fluoro complex, only in Teflon tubes, whereas
the use of glass vessels led to [Ir(C8H12)(PPh3)2][SiF5]. The
X-ray diffraction analysis of this iridium() complex salt
shows that the rather unstable [SiF5]Ϫ anion can be trapped.
Once compound 3 has been isolated it does not interact
with the glass surface. Evidence for that is derived from
NMR and IR spectroscopic data obtained from the oily
residue, formed in a glass vessel, as a result of the decompo-
sition of 3 after some weeks. In the 19F NMR spectrum a
triplet (δ ϭ Ϫ256.3 ppm, t, J ϭ 28.8 Hz) and in the 31P{H}
NMR spectrum a doublet (δ ϭ 24.5 ppm, d, J ϭ 28.7 Hz)
suggest the formation of a complex, which has one fluorine
atom and two phosphane groups bonded to the iridium
Experimental Section
General Remarks: Solvents were dried and distilled under nitrogen
prior to use. All reactions were carried out under dry nitrogen,
using standard Schlenk techniques. NMR spectra were recorded
using a Bruker Avance 200, Bruker MSL 400 or a Bruker Avance
500 spectrometer and referenced to the resonances of the residual
atom. The IR spectrum exhibits a band at 1945 cmϪ1 at- protons in deuterated benzene or CD2Cl2. 1H NMR: external
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Eur. J. Inorg. Chem. 2004, 2678Ϫ2682

Synthesis of a Novel Organoiridium(I) Fluoro Complex
FULL PAPER
Table 1. Crystallographic data for 3 and 4
3 (incl. THF)
4 (incl. CH2Cl2)
Empirical formula
C28H31FIrPO0.5
617.70
200(2)
71.073
monoclinic
P21/n
931.9(3)
1629.4(7)
1592.9(7)
90
92.85(3)
90
2.4157(17)
4
5.616
C45H44Cl2F5IrP2Si
1032.93
200(2)
71.073
monoclinic
P21/c
1157.4(9)
1864.4(9)
1922.5(17)
90
96.16(7)
90
4.125(5)
4
3.529
Molecular mass [gmolϪ1
]
Temperature [K]
Wavelength λ [pm]
Crystal system
Space group
a [pm]
b [pm]
c [pm]
α [°]
β [°]
γ [°]
V [nm3]
Z
Absorption coefficient [mmϪ1
F(000)
]
1216
2056
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I Ͼ 2σ(I)]
5803
7556
4216 [Rint ϭ 0.0421]
4216/0/292
1.111
0.0560, 0.1471
5.144/Ϫ3.777
7149 [Rint ϭ 0.1654]
7149/0/505
1.050
0.0671, 0.1620
3.414/Ϫ2.480
Ϫ3
˚
Largest diff. Peak/hole [e·A
]
standard TMS. 13C NMR: external standard TMS. 19F NMR: ex-
H, CH), 7.39 (m, 15 H, C6H5) ppm. 13C NMR (125.77 MHz,
ternal standard CCl3F. 31P NMR: external standard 85% H3PO4. CD2Cl2): δ ϭ 31.4 (s, C-3, C-4, C-7, C-8), 87.4 (t, J ϭ 5.6 Hz, C-
Infrared spectra were recorded on a BIO-RAD Digilab FTS 7 spec-
1, C-2, C-5, C-6), 128.9 (t, J ϭ 5.2 Hz, C6H5), 131.7 (t, J ϭ 1.0 Hz,
C6H5), 134.6 (t, J ϭ 5.5 Hz, C6H5) ppm. 19F NMR (188.27 MHz,
trometer. [Ir(µ-OH)(C8H12)]2 (1) was prepared by literature meth-
ods.[21] All other materials used in the syntheses were reagent grade CCl3F): δ ϭ Ϫ139.1 (s, SiF5) ppm. 31P NMR (121.50 MHz,
chemicals and used without further purification.
CD2Cl2): δ ϭ 17.8 (s, IrP2) ppm. FABϩMS 70 eV, m/z (rel. int.):
825 [Ir(C8H12)(PPh3)2] (100). FABϪMS 70 eV, m/z (rel. int.): 123
[SiF5] (100).
IrF(C8H12)(PPh3) (3): Aqueous HF (50.0 µL, 2.00 mmol, 73%)
solution was added to a solution of 1 (0.63 g, 1.00 mmol) in THF
(10 mL). The reaction mixture was allowed to stand overnight to
form a yellow insoluble precipitate 2, which was filtered off and
dried in vacuo. The solid was treated with a solution of PPh3
(0.52 g, 2.00 mmol) in THF (10 mL) and the mixture was stirred
until all solids had dissolved. The resulting reddish solution was
layered with pentane (40 mL). After standing overnight orange
crystals had formed which were filtered off and dried under re-
duced pressure. The product was recrystallised from THF/pentane
(0.83 g, 71%). M.p. 218 °C (decomp.). C26H27FIrP (581.68): calcd.
C 53.69, H 4.68; found C 53.47, H 4.81. 1H NMR (300.13 MHz,
C6D6): δ ϭ 1.40 (m, 4 H, CH2), 2.05 (m, 4 H, CH2), 2.59 (m, 2 H,
CH), 5.42 (m, 2 H, CH), 7.08 (m, 9 H, C6H5), 7.93 (m, 6 H, C6H5)
ppm. 19F NMR (188.27 MHz, CCl3F): δ ϭ Ϫ219.3 (s, IrF) ppm.
31P NMR (121.50 MHz, C6D6): δ ϭ 25.1 (s, IrP). EIMS 70 eV,
m/z (rel. int.): 582 [M] (5), 262 [M Ϫ IrϪC8H12ϪF] (100), 108
[M Ϫ IrϪP(C6H5)3ϪF] (20).
X-ray Crystallographic Study: The single crystals were mounted on
a glass fibre in a frozen paraffin drop. Diffraction data were col-
lected on a STOE AED2 four-circle diffractometer with graphite-
monochromated Mo-Kα radiation (λ ϭ 71.073 pm). The crystal
structures were solved by direct methods using SHELXS-97[26] and
refined with SHELXL-97[27] against F2 for all data by full-matrix
least-squares. All non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were included in the model at fixed positions. A
summary of the crystal data is given in Table 1.
CCDC-228254 (for 3) and -228255 (for 4) contain the supplemen-
tary crystallographic data for this paper. These data can be ob-
tained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html
[or from the Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge CB2 1EZ, UK; Fax: (internat.) ϩ44-1223-336-
033; E-mail: deposit@ccdc.cam.ac.uk].
[Ir(C8H12)(PPh3)2][SiF5] (4): Aqueous HF (0.50 mL, 20.0 mmol,
73%) solution was added to a solution of 1 (0.63 g, 1.00 mmol) in
THF (10 mL) in a glass vessel . The reaction mixture was allowed
to stand overnight to form a yellow insoluble precipitate, which
was filtered off and dried in vacuo. The solid was treated with a
solution of PPh3 (1.05 g, 4.00 mmol) in THF (10 mL) and the mix-
ture was stirred for 24 h. Deep red crystals formed which were fil-
tered off and dried under reduced pressure. The product was recrys-
tallised from CH2Cl2/pentane (1.80 g, 96%). C44H42F5IrP2Si
(948.05): calcd. C 55.74, H 4.47; found C 55.41, H 4.65. IR (CsI):
Acknowledgments
This work was supported by the Deutsche Forschungsgemein-
schaft, the Degussa-Hüls AG, the Fonds der Chemischen Industrie,
and the Göttinger Akademie der Wissenschaften.
[1]
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