(η5-Pentamethylcyclopentadienyl)iridium(III) complexes with η2-N,O and η2-P,S ligands

Article abstract of DOI:10.1002/ejic.200500528

Chloro(η⁵-pentamethylcyclopentadienyl)(η²- pyridine-2-carboxylato)iridium(III) [Ir(η⁵-C₅Me ₅)(η²-C₅H₄N-2-CO₂)Cl] (2) and chloro(η⁵-pentamethylcyc

Full text of DOI:10.1002/ejic.200500528

FULL PAPER
DOI: 10.1002/ejic.200500528
(η5-Pentamethylcyclopentadienyl)iridium(III) Complexes with η2-N,O and
η2-P,S Ligands
Michael Gorol,[a] Herbert W. Roesky,*[a] Mathias Noltemeyer,[a] and Hans-Georg Schmidt[a]
Keywords: Cyclopentadienyl ligands / Iridium / N,O ligands / P,S ligands
Chloro(η5-pentamethylcyclopentadienyl)(η2-pyridine-2-car-
boxylato)iridium(III) [Ir(η5-C5Me5)(η2-C5H4N-2-CO2)Cl] (2)
and chloro(η5-pentamethylcyclopentadienyl)[η2-2-(diphenyl-
phosphanyl)thiophenolato]iridium(III) [Ir(η5-C5Me5)(η2-2-
Ph2PC6H4S)Cl] (3) were prepared and their structures deter-
mined by single-crystal X-ray diffraction analysis. Complex
2 crystallizes in the orthorhombic space group Pbca. The
number of molecules per unit cell is eight, whereas 3 crys-
tallizes in the orthorhombic space group Pna21 and the
number of molecules per unit cell is four. The coordination
of the η2-bound ligands in 2 and 3 leads to chelate bite angles
N–Ir–O(2) and P–Ir–S of 77.0(2)° and 82.42(7)°, respectively.
The iridium atoms in 2 and 3 are chiral and both enantiomers
are present in the unit cell. The substitution of the chloro
ligand in 3 affords hydrido(η5-pentamethylcyclopentadi-
enyl)-[η2-2-(diphenylphosphanyl)thiophenolato]iridium(III
]
[Ir(η5C5Me5)(η2-2-Ph2PC6H4S)H] (4) and methyl(η5-penta-
methylcyclopentadienyl)[η2-2-(diphenylphosphanyl)thiophen-
olato]iridium(III) [Ir(η5-C5Me5)(η2-2-Ph2PC6H4S)Me] (5),
respectively, in good yields. The 31P{1H} NMR resonances of
4 (δ = 33.9 ppm) and 5 (δ = 35.8 ppm) prove unambiguously
that the 2-(diphenylphosphanyl)thiophenolato ligand still re-
mains η2-coordinated.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
to ensure retention of the thiolate. Accordingly, the two
compounds [Ir(η2-P,S)(Cl)2(PMePh2)2] and [Ir(η2-P,S)3]·
0.75CH2Cl2 have been observed.[7] In addition, an increased
stability due to the chelate effect has been observed for the
iridium(i) complex [Ir(η2-P,S)(CO)(PPh3)].[8]
Introduction
The chemistry of (η5-pentamethylcyclopentadienyl)iridi-
um(iii) complexes has been extensively investigated during
the last few decades.[1] However, there are only a few com-
pounds that contain anionic η2-coordinated ligands (η2-
A,B), of which α-amino acid complexes are the best-known
examples.[2,3] The main aspect of research in this field is
focused on the chiral-at-metal behavior of the isolated com-
plexes. However, in general, the diastereoselectivity is low
and, due to the configurational instability at the metal cen-
ter, epimerization reactions occur in solution.[4] Pyridine-2-
carboxylic acid is an analog to amino acids and is commer-
cially available. Examples of η2-coordinated pyridine-2-car-
boxylato ligands (η2-N,O) applied in organoiridium chemis-
try are [Ir(η5-C5Me5)(η2-N,O)(OH2)]+ and [Ir(η5-
C5Me5)(η2-N,O)]3(ClO4)3, although they were structurally
not characterized.[5]
Stable thiolato complexes have for some time also been
of special interest. Dimeric iridium(i) complexes with bridg-
ing thiolato ligands, for example, have been intensely exam-
ined for their catalytic activity in hydroformylation reac-
tions.[6] However, the elimination of the free thiol by reac-
tion with dihydrogen has proved problematic. Chelating
phosphanyl-thiolate ligands, like the 2-(diphenylphos-
A particular objective of our research in organoiridium
chemistry is the synthesis of stable monomeric complexes
with a defined reaction center that allows further reactions.
Thus, these compounds are useful as starting materials in
the search for new applications in preparative chemistry as
well as in catalysis. We present here the syntheses, charac-
terizations, and crystal-structure analyses of the thus far un-
known chloro(η5-pentamethylcyclopentadienyl)iridium(iii)
complexes [Ir(η5-C5Me5)(η2-C5H4N-2-CO2)Cl] (2) and
[Ir(η5-C5Me5)(η2-2-Ph2PC6H4S)Cl] (3), which contain η2-
coordinated pyridine-2-carboxylato (η2-N,O) and 2-(di-
phenylphosphanyl)thiophenolato (η2-P,S) ligands, respec-
tively. The substitution of the chloro ligand in 3 by a hy-
dride ion and a methyl group are described too, and the
analytical data are given.
Results and Discussion
The reaction of di-μ-chlorobis[chloro(η5-pentamethylcy-
phanyl)thiophenolato ligand (η2-P,S), have been introduced clopentadienyl)iridium(iii)] [Ir2(η5-C5Me5)2(μ-Cl)2Cl2] (1)
with sodium pyridine-2-carboxylate in methanol or sodium
[a] Institut für Anorganische Chemie der Universität Göttingen,
2-(diphenylphosphanyl)thiophenolate in tetrahydrofuran
Tammannstr. 4, 37077 Göttingen, Germany
gives the orange crystalline compounds chloro(η5-penta-
Fax: + 49-551-393373
E-mail: hroesky@gwdg.de
methylcyclopentadienyl)(η2-pyridine-2-carboxylato)iri-
4840
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(η5-Pentamethylcyclopentadienyl)iridium(iii) Complexes with η2-N,O and η2-P,S Ligands
FULL PAPER
dium(iii) [Ir(η5-C5Me5)(η2-C5H4N-2-CO2)Cl] (2) in 89% at δ = 84.9 ppm and those of the methyl groups at δ =
yield and chloro(η5-pentamethylcyclopentadienyl)[η2-2-(di- 8.3 ppm. The corresponding resonances of compound 3 are
phenylphosphanyl)thiophenolato]iridium(iii) [Ir(η5-C5Me5)- observed at δ = 92.9 ppm (d, JC,P = 3 Hz) and δ = 8.2 ppm
(η2-2-Ph2PC6H4S)Cl] (3) in 72% yield, respectively (d, JC,P = 1 Hz). The 31P{1H} NMR spectrum of 3 shows
(Scheme 1).
a resonance at δ = 30.4 ppm, which is strongly shifted
downfield (Δδ = 43.5 ppm) in comparison to the free phos-
phane (δ = –13.1 ppm).[9]. This is in agreement with the
coordination shift typical for the 31P NMR resonances of
five-membered rings.[10]
The bands at ν = 253 and 267 cm–1 in the IR spectra of
˜
2 and 3 can be assigned to the absorptions of the Ir–Cl
stretching modes.
Single crystals suitable for X-ray diffraction analysis were
obtained by slow diffusion of diethyl ether into a saturated
solution of 2 in dichloromethane. Compound 2 crystallizes
in the orthorhombic space group Pbca. Figure 1 shows the
molecular structure of [Ir(η5-C5Me5)(η2-C5H4N-2-CO2)Cl]
(2) together with selected bond lengths and angles. The Ir–
Cl [239.97(15) pm] and Ir–N [208.8(7) pm] bonds are
shorter than in the l-prolinato complex [Ir(η5-C5Me5)(l-
ProO)Cl] [Ir(1)–Cl(1) = 241.7(2), Ir(2)–Cl(2) = 240.6(3),
Ir(1)–N(1) = 212.8(7), and Ir(2)–N(2) = 213.1(7) pm],[2]
which is probably due to the π-acceptor properties of the
pyridine ring in 2. The coordination of the η2-bound pyri-
dine-2-carboxylate leads to an N–Ir–O(2) bond angle of
77.0(2)°, which is similar to that of 77.7(1)° in the corre-
Scheme 1.
The resonances of the protons of the η5-C5Me5 groups
appear in the 1H NMR spectrum of 2 as a singlet (δ =
1.63 ppm, 15 H) and that of 3 as a doublet (δ = 1.56 ppm,
JH,P = 2.2 Hz, 15 H). In the 13C NMR spectrum of 2, the
resonances of the η5-C5Me5 ring carbon atoms are found
Figure 1. Molecular structure of [Ir(η5-C5Me5)(η2-C5H4N-2-CO2)
Cl] (2) with 50% probability ellipsoids and the labelling scheme;
selected bond lengths [pm] and angles [°]: Ir–Cl 239.97(15), Ir–N
208.8(7), Ir–O(2) 210.1(5), O(1)–C(11) 122.5(9), O(2)–C(11)
127.9(10); C(1)–Ir–C(2) 37.2(3), C(1)–Ir–C(3) 64.8(3), C(1)–Ir–Cl
Figure 2. Molecular structure of [Ir(η5-C5Me5)(η2-2-Ph2PC6H4S)
Cl] (3) with 50% probability ellipsoids and the labelling scheme;
selected bond lengths [pm] and angles [°]: Ir–Cl 241.93(18), Ir–P
160.8(3), C(2)–Ir–C(3) 39.2(3), C(2)–Ir–Cl 129.8(2), C(3)–Ir–Cl 227.32(18), Ir–S 238.0(2); C(1)–Ir–C(3) 63.7(3), C(1)–Ir–C(4)
96.92(19), C(4)–Ir–C(1) 66.2(3), C(4)–Ir–C(2) 65.5(3), C(4)–Ir–C(3) 64.0(3), C(1)–Ir–Cl 126.9(2), C(1)–Ir–P 103.2(2), C(1)–Ir–S
39.1(3), C(4)–Ir–C(5) 39.2(3), C(4)–Ir–Cl 96.16(17), C(5)–Ir–C(1)
40.8(3), C(5)–Ir–C(2) 65.5(2), C(5)–Ir–C(3) 65.7(3), C(5)–Ir–Cl
128.03(18), C(11)–O(2)–Ir 117.7(4), N–Ir–C(1) 111.7(3), N–Ir–C(2)
143.0(2), C(2)–Ir–C(1) 37.6(3), C(2)–Ir–C(3) 38.2(3), C(2)–Ir–C(4)
63.0(3), C(2)–Ir–Cl 95.1(2), C(2)–Ir–P 127.0(2), C(2)–Ir–S 150.3(2),
C(3)–Ir–Cl 94.5(2), C(3)–Ir–P 165.1(2), C(3)–Ir–S 112.3(2), C(4)–
144.5(3), N–Ir–C(3) 166.1(3), N–Ir–C(4) 127.0(3), N–Ir–C(5) Ir–C(3) 37.1(3), C(4)–Ir–Cl 125.7(2), C(4)–Ir–P 145.7(2), C(4)–Ir–
102.5(3), N–Ir–Cl 84.55(15), N–Ir–O(2) 77.0(2), O(1)–C(11)–O(2) S 90.67(18), C(5)–Ir–C(1) 38.9(3), C(5)–Ir–C(2) 64.3(3), C(5)–Ir–
125.2(7), O(2)–Ir–C(1) 107.9(3), O(2)–Ir–C(2) 95.4(2), O(2)–Ir– C(3) 64.5(3), C(5)–Ir–C(4) 39.2(3), C(5)–Ir–Cl 157.9(2), C(5)–Ir–P
C(3) 116.9(2), O(2)–Ir–C(4) 156.0(2), O(2)–Ir–C(5) 146.9(2), O(2)– 110.4(2), C(5)–Ir–S 104.5(2), P–Ir–Cl 88.02(6), P–Ir–S 82.42(7), S–
Ir–Cl 85.02(14).
Ir–Cl 89.45(8).
Eur. J. Inorg. Chem. 2005, 4840–4844
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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4841

M. Gorol, H. W. Roesky, M. Noltemeyer, H.-G. Schmidt
FULL PAPER
sponding rhodium(iii) complex [Rh(η5-C5Me5)(η2-C5H4N- methyl groups at δ = 9.1 ppm (d, JC,P = 0.8 Hz). The corre-
2-CO2)Cl].[11]
sponding resonances of compound 5 appear at δ = 92.8 (d,
Slow cooling of a hot solution of 3 in toluene gave single JC,P = 3.3 Hz) and 8.20 ppm (d, JC,P = 1.0 Hz). The reso-
crystals suitable for X-ray diffraction analysis. Compound nance of the methyl group bound to the iridium atom is
3 crystallizes in the orthorhombic space group Pna21. Fig- observed at δ = –17.4 ppm (d, JC,P = 8.4 Hz). The 31P{1H}
ure 2 shows the molecular structure of [Ir(η5-C5Me5)(η2-2- NMR spectrum of 4 shows a resonance at δ = 33.9 ppm
Ph2PC6H4S)Cl] (3) together with selected bond lengths whereas that of 5 appears at δ = 35.8 ppm. In comparison
and angles.
Ph2PC6H4S)(PMePh2)2] [Ir–P(1)
240.1(1), Ir–Cl(1) = 238.42(9), Ir–Cl(2) = 237.36(9) pm; P– phenolato ligand still remains η2-coordinated.
Ir–S = 81.06(3)°][7] the Ir–P [227.32(18) pm] and Ir–S In the IR spectrum of 4, the band at ν = 2102 cm–1 is
In
comparison
with
236.1(1), Ir–S
[Ir(Cl)2(η2-2- to the free ligand (δ = –13.1 ppm),[9] this strong downfield
shift is good evidence that the 2-(diphenylphosphanyl)thio-
=
=
˜
[238.0(2) pm] bonds are shorter and the Ir–Cl bond characteristic of absorptions of the Ir–H stretching
[241.93(18) pm] is longer. The deviation from 90°, with a P– modes.[12]
Ir–S bond angle of 82.42(7)°, is of the same order of magni-
tude and is not as clear as that in 2. The geometry in both
2 and 3 can be described as pseudo-octahedral coordination
Conclusions
of the iridium atom in which the η5-C5Me5 group occupies
The cleavage of the chloro bridges in [Ir2(η5-C5Me5)2(μ-
three fac coordination sides. The metal coordination sphere
Cl)2Cl2] (1) by η2-A,B ligands affords stable monomeric
chelate complexes. Thus, the reactions of 1 with pyridine-2-
carboxylate and 2-(diphenylphosphanyl)thiophenolate yield
is completed by an η2-coordinated ligand and a chlorine
atom (the bond angles at the iridium atom are listed in the
captions of Figures 1 and 2). In each case, the iridium atom
is chiral and both enantiomers are present in the unit cell.
[Ir(η5-C5Me5)(η2-C5H4N-2-CO2)Cl]
(2)
and
[Ir(η5-
C5Me5)(η2-2-Ph2PC6H4S)Cl] (3), respectively. The X-ray
diffraction analyses show that the geometry of both com-
plexes can be described as pseudo-octahedral coordination
of the iridium atom in which the η5-C5Me5 group occupies
three fac coordination sides. In each case the complex is
chiral at the iridium atom and both enantiomers are present
in the unit cell. The complexes [Ir(η5-C5Me5)(η2-2-
Ph2PC6H4S)H] (4) and [Ir(η5-C5Me5)(η2-2-Ph2PC6H4S)Me]
(5) are easily accessible by substitution of the chloro ligand
in 3. According to the 31P NMR spectra, the 2-(diphenyl-
phosphanyl)thiophenolato ligand remains η2-coordinated
in both compounds. The hydrido complex 4 and the methyl
compound 5 are useful derivatives for further investigations.
Substitution Reactions
Substitution of the chloro ligand by a hydride ion or a
methyl group was achieved successfully only for 3. Thus,
the reaction of [Ir(η5-C5Me5)(η2-2-Ph2PC6H4S)Cl] (3) with
LiAlH4 or MeLi in tetrahydrofuran results, after removal
of the solvent and subsequent extraction with hexane, in
the corresponding hydrido complex hydrido(η5-penta-
methylcyclopentadienyl)[η2-2-(diphenylphosphanyl)thio-
phenolato]iridium(iii) [Ir(η5-C5Me5)(η2-2-Ph2PC6H4S)H]
(4) in 91% yield and the methyl compound methyl(η5-
pentamethylcyclopentadienyl)[η2-2-(diphenylphosphanyl)-
thiophenolato]iridium(iii) [Ir(η5-C5Me5)(η2-2-Ph2PC6H4S)-
Me] (5) in 87% yield, respectively (Scheme 2).
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, a Bruker MSL 400, or a Bruker Avance
500 spectrometer and referenced to the resonances of the residual
1
protons in [D6]DMSO, CDCl3, or C6D6. H NMR: external stan-
dard TMS. 13C NMR: external standard TMS. 31P NMR: external
standard 85% H3PO4. Infrared spectra were recorded with a BIO-
RAD Digilab FTS 7 spectrometer. [Ir2(η5-C5Me5)2(μ-Cl)2Cl2] (1)
Scheme 2.
[13]
and 2-Ph2PC6H4SH[9] were prepared by literature methods. All
The resonances of the protons of the η5-C5Me5 groups
other materials used in the syntheses were reagent grade chemicals
and used without further purification.
1
in the H NMR spectrum of 4 appear, due to the coupling
to the iridium-bound hydrido ligand, as a doublet of doub-
lets (δ = 1.62 ppm, JH,P = 2.0, JH,H = 0.8 Hz, 15 H) and
those of 5 as a doublet (δ = 1.57 ppm, JH,P = 1.9 Hz, 15
H). The resonances of the hydrido ligand in 4 and of the
methyl group in 5 are observed as doublets at high field at
δ = –15.37 (d, 2JH,P = 36.0 Hz, 1 H) and –0.22 ppm (d, 3JH,P
= 6.1 Hz, 3 H), respectively. In the 13C NMR spectrum of
4, the resonance of the η5-C5Me5 ring carbon atoms is
[Ir(η5-C5Me5)(η2-C5H4N-2-CO2)Cl] (2): A mixture of 1 (0.80 g,
1.00 mmol), C5H4N-2-CO2H (0.26 g, 2.12 mmol), and NaOEt
(0.12 g, 2.22 mmol) in methanol (70 mL) was heated under reflux
for 3 h and finally filtered hot through Celite. The solution was
concentrated under reduced pressure to 20 mL. The resulting
orange crystalline solid was filtered off, washed with diethyl ether
(2×10 mL), and dried in vacuo (0.85 g, 89%). M.p. 270 °C (de-
comp.). C16H19ClIrNO2 (485.00): calcd. C 39.62, H 3.95, Cl 7.31,
4
4
4
found at δ = 93.2 ppm (d, JC,P = 3.1 Hz) and that of the N 2.89; found C 39.59, H 4.01, Cl 7.39, N 2.96. IR (CsI): ν = 253
˜
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(η5-Pentamethylcyclopentadienyl)iridium(iii) Complexes with η2-N,O and η2-P,S Ligands
FULL PAPER
1
(Ir–Cl) cm–1. H NMR (500.13 MHz, [D6]DMSO): δ = 8.77 (d, J ppm. 31P NMR (202.46 MHz, C6D6): δ = 33.9 (s, IrP) ppm. EIMS
= 6.0 Hz, 1 H, C5H4NCO2), 8.12 (t, J = 5.0 Hz, 1 H, C5H4NCO2), (70 eV): m/z (%) = 622 (100) [M], 607 (50) [M – H – CH2].
7.90 (d, J = 8.0 Hz, 1 H, C5H4NCO2), 7.75 (t, J = 7.0 Hz, 1 H,
[Ir(η5-C5Me5)(η2-2-Ph2PC6H4S)Me] (5): A solution of 3 (0.26 g,
C5H4NCO2), 1.63 (s, 15 H, C5Me5) ppm. 13C NMR (125.77 MHz,
0.40 mmol) in THF (10 mL) was treated with MeLi (0.30 mL,
[D6]DMSO): δ = 171.7 (C5H4NCO2), 150.5 (C5H4NCO2), 150.3
0.48 mmol, 1.6 m in hexane), stirred at room temperature for 12 h,
(C5H4NCO2), 139.6 (C5H4NCO2), 129.1 (C5H4NCO2), 126.2
and subsequently filtered through Celite. The solvent was removed
(C5H4NCO2), 84.9 (C5Me5), 8.3 (C5Me5) ppm. EIMS (70 eV): m/z
from the filtrate under reduced pressure and the resulting residue
(%) = 485 (40) [M], 449 (60) [M – H – Cl], 362 (100) [M – C5H4N-
was extracted with hexane (2×40 mL). The removal of the solvent
2-CO2 – H].
from the combined extracts in vacuo resulted in the title compound
as
a yellow powder (0.22 g, 87%). M.p. 240 °C (decomp.).
[Ir(η5-C5Me5)(η2-2-Ph2PC6H4S)Cl] (3):
A
solution of 2-
C29H32IrPS (635.82): calcd. C 54.78, H 5.07; found C 54.71, H
Ph2PC6H4SH (0.59 g, 2.00 mmol) in THF (30 mL) together with
surplus sodium (approx. 200 mg) was stirred at room temperature
until the evolution of hydrogen ceased. After filtration, the filtrate
was added dropwise to a solution of 1 (0.80 g, 1.00 mmol) in THF
(30 mL). The reaction mixture was stirred for an additional 3 h
and, subsequently, the solvent was removed under reduced pres-
sure. The residue was crystallized from dichloromethane/diethyl
ether (1:4). The reddish crystals obtained accordingly were filtered
off and dried in vacuo (0.95 g, 72%). M.p. 325 °C. C28H29ClIrPS
(656.24): calcd. C 51.25, H 4.45, P 4.72; found C 50.64, H 4.47, P
5.02. 1H NMR (200.13 MHz, CDCl3): δ = 7.64 (m, 1 H,
Ph2PC6H4S), 7.46 (m,
Ph2PC6H4S), 6.95 (m,
5
2
H, Ph2PC6H4S), 7.24 (m,
H, Ph2PC6H4S), 6.70 (m,
5
1
H,
H,
Ph2PC6H4S), 1.57 (d, 4JH,P = 1.9 Hz, 15 H, C5Me5), –0.22 (d, 3JH,P
= 6.1 Hz, 3 H, IrMe) ppm. 13C NMR (125.77 MHz, CDCl3): δ =
157.6 (d, JC,P = 26.2 Hz, Ph2PC6H4S), 137.7 (d, JC,P = 50.1 Hz,
Ph2PC6H4S), 133.9 (d, JC,P = 3.2 Hz, Ph2PC6H4S), 133.0 (d, JC,P
= 9.7 Hz, Ph2PC6H4S), 131.8 (d, JC,P = 10.7 Hz, Ph2PC6H4S),
128.3 (d, JC,P = 10.7 Hz, Ph2PC6H4S), 120.7 (d, JC,P = 6.9 Hz,
2
3
Ph2PC6H4S), 92.8 (d, JC,P = 3.3 Hz, C5Me5), 8.2 (d, JC,P
=
4.31.[14] IR (CsI): ν = 267 (Ir–Cl) cm–1. 1H NMR (500.13 MHz,
˜
1.0 Hz, C5Me5), –17.4 (d, JC,P = 8.4 Hz, IrMe) ppm. 31P NMR
(202.46 MHz, CDCl3): δ = 35.8 (s, IrP) ppm. EIMS (70 eV): m/z
(%) = 636 (10) [M], 621 (100) [M – CH3], 607 (5) [M – CH3–CH2].
CDCl3): δ = 7.97 (m, 2 H, Ph2PC6H4S), 7.62 (dd, 1J = 7.9, 2J =
3.4 Hz, 1 H, Ph2PC6H4S), 7.49 (m, 3 H, Ph2PC6H4S), 7.28 (m, 5
1
1
H, Ph2PC6H4S), 7.13 (t, J = 8.2 Hz, 1 H, Ph2PC6H4S), 6.99 (t, J
= 7.4 Hz, 1 H, Ph2PC6H4S), 6.72 (t, 1J = 7.4 Hz, 1 H, Ph2PC6H4S),
X-ray Crystallographic Study: The single crystals were mounted on
a glass fiber in a frozen drop of paraffin. Diffraction data were
collected with a STOE AED2 four-circle diffractometer with graph-
ite-monochromated Mo-Kα radiation (λ = 71.073 pm). The crystal
structures were solved by direct methods using SHELXS-97[15] and
refined with SHELXL-97[16] against F2 on all data by full-matrix
least squares. All non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were included in the model at fixed positions
(Table 1). CCDC-272324 (2) and -272325 (3) contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
4
1.56 (d, JH,P
2.2 Hz, 15 H, C5Me5) ppm. 13C NMR
=
(125.77 MHz, CDCl3): δ = 155.5 (d, JC,P = 23.4 Hz, Ph2PC6H4S),
136.2 (d, JC,P = 52.9 Hz, Ph2PC6H4S), 135.8 (d, JC,P = 10.6 Hz,
Ph2PC6H4S), 134.8 (d, JC,P = 70.6 Hz, Ph2PC6H4S), 132.0 (d, JC,P
= 3.7 Hz, Ph2PC6H4S), 131.7 (d, JC,P = 9.5 Hz, Ph2PC6H4S), 131.2
(d, JC,P
= 2.7 Hz, Ph2PC6H4S), 130.7 (d, JC,P = 2.6 Hz,
Ph2PC6H4S), 130.0 (d, JC,P = 2.6 Hz, Ph2PC6H4S), 128.8 (d, JC,P
= 10.4 Hz, Ph2PC6H4S), 128.1 (d, JC,P = 10.9 Hz, Ph2PC6H4S),
128.0 (d, JC,P = 10.2 Hz, Ph2PC6H4S), 126.1 (d, JC,P = 58.5 Hz,
2
Ph2PC6H4S), 122.1 (d, JC,P = 7.6 Hz, Ph2PC6H4S), 92.9 (d, JC,P
3
= 3 Hz, C5Me5), 8.2 (d, JC,P = 1.0 Hz, C5Me5) ppm. 31P NMR
(202.46 MHz, CDCl3): δ = 30.4 (s, IrP) ppm. EIMS (70 eV): m/z
(%) = 656 (8) [M], 621 (100) [M – Cl].
[Ir(η5-C5Me5)(η2-2-Ph2PC6H4S)H] (4): A solution of 3 (0.66 g,
1.01 mmol) in THF (20 mL) was treated with LiAlH4 (0.04 g,
1.05 mmol), stirred at room temperature for 12 h, and subsequently
filtered through Celite. The solvent was removed from the filtrate
under reduced pressure and the resulting residue was extracted with
hexane (2×60 mL). The removal of the solvent from the combined
extracts in vacuo afforded the title compound as a yellow powder
(0.57 g, 91%). M.p. 240 °C (decomp.). C28H30IrPS (621.79): calcd.
Table 1. Crystallographic data for 2 and 3.
2
3
Empirical formula
Formula mass [gmol–1]
Temperature [K]
Wavelength λ [pm]
Crystal system
Space group
a [pm]
C16H19ClIrNO2
484.97
203(2)
71.073
orthorhombic
Pbca
1429.4(3)
1457.9(4)
1468.1(5)
3.0595(14)
8
C28H29ClIrPS
656.19
133(2)
71.073
orthorhombic
Pna21
1655.0(3)
1019.6(2)
1456.3(3)
2.4574(8)
4
C 54.09, H 4.86; found C 53.71, H 4.80. IR (CsI): ν = 2102 (Ir–H)
˜
1
1
1
cm–1. H NMR (500.13 MHz, C6D6): δ = 7.99 (dd, J = 11.5, J =
8.1 Hz, 2 H, Ph2PC6H4S), 7.91 (dd, 1J = 8.1, 2J = 3.5 Hz, 1 H,
b [pm]
c [pm]
Ph2PC6H4S), 7.21 (m,
3 H, Ph2PC6H4S), 7.11 (m, 3 H,
Volume [nm3]
Z
1
Ph2PC6H4S), 6.93 (m, 3 H, Ph2PC6H4S), 6.76 (t, J = 7.0 Hz, 1 H,
Ph2PC6H4S), 6.57 (t, 1J = 7.0 Hz, 1 H, Ph2PC6H4S), 1.62 (dd, 4JH,P
Absorption coefficient
8.906
5.707
4
= 2.0, JH,H = 0.8 Hz, 15 H, C5Me5), –15.37 (d, 2JH,P = 36.0 Hz, 1
[mm–1]
H, IrH) ppm. 13C NMR (125.77 MHz, C6D6): δ = 160.8 (d, JC,P
=
F(000)
Reflections collected
Independent reflections
1856
5382
2691 (Rint
1288
31373
7149 (Rint
0.1654)
5681/1/296
1.081
26.9 Hz, Ph2PC6H4S), 138.0 (d, JC,P = 46.9 Hz, Ph2PC6H4S), 135.4
(d, JC,P = 62.7 Hz, Ph2PC6H4S), 135.3 (d, JC,P = 69.5 Hz,
Ph2PC6H4S), 134.6 (d, JC,P = 11.2 Hz, Ph2PC6H4S), 132.2 (d, JC,P
= 3.7 Hz, Ph2PC6H4S), 131.6 (d, JC,P = 10.5 Hz, Ph2PC6H4S),
129.9 (d, JC,P = 2.5 Hz, Ph2PC6H4S), 129.3 (d, JC,P = 2.4 Hz,
Ph2PC6H4S), 128.7 (d, JC,P = 2.4 Hz, Ph2PC6H4S), (127.8, 127.7,
127.5 overlaps from C6D6), 120.4 (d, JC,P = 7.2 Hz, Ph2PC6H4S),
=
=
0.1867)
Data/restraints/parameters 2691/339/189
Goodness-of-fit on F2
1.065
Final R indices [I Ͼ 2σ(I)] 0.0462, 0.1169
0.0399, 0.0924
7.323/–1.967
Largest diff. peak/hole
2.130/–3.595
[eÅ–3]
2
3
93.2 (d, JC,P = 3.1 Hz, C5Me5), 9.1 (d, JC,P = 0.8 Hz, C5Me5)
Eur. J. Inorg. Chem. 2005, 4840–4844
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4843

M. Gorol, H. W. Roesky, M. Noltemeyer, H.-G. Schmidt
FULL PAPER
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Acknowledgments
This work was supported by the Degussa–Hüls AG, the Fonds der
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Received: June 14, 2005
Published Online: October 18, 2005
4844
www.eurjic.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2005, 4840–4844