Acyliridium-alkoxycarbenes and an iridacycle containing vinyl acetate (-C(=CH2)OC(CH3)O-) ligand from reactions of acetatoiridium with alkynes

Article abstract of DOI:10.1021/om0302746

Acyliridium-alkoxycarbenes [Ir(=C(OR′)CH ₃)(C(=O)R)(η²-O₂CCH₃)(PPh ₃)₂]OTf(3, R = CH₃, R′ = CH₃ (a), R = CH₃, R′ = CH₂CH₃ (b), R = CH₂Ph, R′ = CH₃ (c), R = CH₂Ph, R′ = CH₂CH₃ (d)) and [Ir(-COCH₂CH ₂CH₂)(C(=O)R)(η²-O₂CCH ₃)(PPh₃)₂]OTf (4, R = CH₃) are obtained from reactions of [Ir(R)(η²-O₂CCH ₃)(CO)(PPh₃)₂]OTf (2, R = CH₃ (a), CH₂Ph (b)) with HC≡CH/R′OH and HC≡CCH ₂CH₂OH, respectively. Complex 2a also undergoes 1,1-insertion reaction of HC≡CH into an Ir-O bond to give an iridacycle containing a vinyl acetate (-C(=CH₂)OC(CH₃)O-) ligand, [Ir(OC(CH₃)OC(=CH₂))(CH₃)(CO)(PPh ₃)₂]OTf (5), in the absence of an alcohol. The methyl group of the alkoxycarbene ligand of 3a is readily transferred to the central metal to give a methyliridium complex and also by PPh3 in solution to give a bis-acyliridium complex. Plausible reaction pathways are suggested for the formation of acyliridium-alkoxycarbenes and the iridacycle containing a vinyl acetate (-C(=CH₂)OC(CH₃)O-) ligand on the basis of the deuterium labeling experiments.

Full text of DOI:10.1021/om0302746

Organometallics 2003, 22, 3239-3244
3239
Acylir id iu m -Alk oxyca r ben es a n d a n Ir id a cycle
Con ta in in g Vin yl Aceta te (-C(dCH2)OC(CH3)O-)
Liga n d fr om Rea ction s of Aceta toir id iu m w ith Alk yn es
Chong Shik Chin,* Mieock Kim, Myung Ki Lee, and Hyungeui Lee
Department of Chemistry, Sogang University, Seoul 121-742, Korea
Received April 15, 2003
Acyliridium-alkoxycarbenes [Ir(dC(OR′)CH3)(C(dO)R)(η2-O2CCH3)(PPh3)2]OTf (3, R ) CH3,
R′ ) CH3 (a ), R ) CH3, R′ ) CH2CH3 (b), R ) CH2Ph, R′ ) CH3 (c), R ) CH2Ph, R′ )
CH2CH3 (d )) and [Ir(dCOCH2CH2CH2)(C(dO)R)(η2-O2CCH3)(PPh3)2]OTf (4, R ) CH3) are
obtained from reactions of [Ir(R)(η2-O2CCH3)(CO)(PPh3)2]OTf (2, R ) CH3 (a ), CH2Ph (b))
with HCtCH/R′OH and HCtCCH2CH2OH, respectively. Complex 2a also undergoes 1,1-
insertion reaction of HCtCH into an Ir-O bond to give an iridacycle containing a vinyl
acetate (-C(dCH2)OC(CH3)O-) ligand, [Ir(OC(CH3)OC(dCH2))(CH3)(CO)(PPh3)2]OTf (5), in
the absence of an alcohol. The methyl group of the alkoxycarbene ligand of 3a is readily
transferred to the central metal to give a methyliridium complex and also by PPh3 in solution
to give a bis-acyliridium complex. Plausible reaction pathways are suggested for the formation
of acyliridium-alkoxycarbenes and the iridacycle containing a vinyl acetate (-C(dCH2)OC-
(CH3)O-) ligand on the basis of the deuterium labeling experiments.
In tr od u ction
cross-conjugated polyenes,4c and dienynes,4d while only
one iridium-carbene4d containing an Ir(CO)(PPh3)2 moi-
ety has been isolated during our studies thus far.4 The
1,1-insertion of alkynes into the Ir-C bond has also
been observed in C-C bond forming reactions involving
IrdC complexes to give conjugated organic compounds
from our studies4c,d and others.5
Reactions of transition metal complexes with alkynes
have been extensively investigated on the basis of the
fact that they produce not only a variety of interesting
organic compounds but also metal-carbenes,2a-d
-vinylidenes,1h,2e-h and -allenylidenes,2i,j which are reac-
tive precursors and intermediates in catalytic processes
such as olefin metathesis and alkyne polymerization.1,2
Iridium-carbenes, -vinylidenes, and -allenylidenes have
been isolated from reactions of iridium with alkynes.3
We have also suggested those IrdC complexes as the
plausible intermediates in reactions of iridium com-
plexes with alkynes to produce various conjugated
organic compounds such as cis-alkenes,4a,b allenes,4b
During our studies on the reactivity of metal com-
plexes with two labile ligands, [Ir(A)(R)(CO)(OH2)-
(PPh3)2](A) (A ) OTf (1), OClO3 (1′); R ) CH3 (a ), CH2Ph
(b)), we found that the two labile ligands (A, OH2) of
1a and 1′a are readily replaced by hydrocarbyl ligands
to give [Ir(CH3)(CHdCHPPh3)2(CO)(PPh3)2](A)24a,6 and
the two (OTf, OH2) ligands of 1 are displaced with a
bidentate O-donor ligand η2-O2CCH3 to give [Ir(R)(η2-
O2CCH3)(CO)(PPh3)2]OTf (2, R ) CH3 (a ), CH2Ph (b)).
We now wish to report the synthesis and reactions of
stable acyliridium-alkoxycarbenes [Ir(dC(OR′)CH3)(C-
(dO)R)(η2-O2CCH3)(PPh3)2]+ (3) that are obtained from
reactions of 2 with HCtCH in the presence of alcohols
(R′OH) and the 1,1-insertion reaction of HCtCH to an
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10.1021/om0302746 CCC: $25.00 © 2003 American Chemical Society
Publication on Web 06/28/2003

3240 Organometallics, Vol. 22, No. 16, 2003
Chin et al.
Sch em e 1
Ir-O bond of 2 to give the iridacycle containing a vinyl
acetate (-C(dCH2)OC(CH3)O-) ligand in the absence
of an alcohol.
F igu r e 1. ORTEP drawing of [Ir(OC(CH3)OC(dCH2))-
(CH3)(CO)(PPh3)2]OTf (5) with 50% thermal ellipsoid prob-
ability. Selected bond distances (Å): Ir1-P1 ) 2.380(2); Ir1-
P2 ) 2.382(2); Ir1-C37 ) 2.181(7); Ir1-C38 ) 1.850(8); Ir1-
C40 ) 2.069(9); Ir1-O2 ) 2.072(6); O1-C38 ) 1.134(9); O2-
C39 ) 1.167(11); C39-C42 ) 1.564(13); O3-C39 ) 1.167(11);
O3-C40 ) 1.535(11); C40-C41 ) 1.288(15). Selected bond
angles (deg): C38-Ir1-C37 ) 91.8(4); C38-Ir1-C40 ) 106.2-
(4); C40-Ir1-O2 ) 79.6(3); O2-Ir1-C37 ) 82.4(3); C38-Ir1-
P2 ) 91.5(3); C38-Ir1-P1 ) 92.1(3); O2-Ir1-P2 ) 88.46(19);
O2-Ir1-P1 ) 88.05(19); C40-Ir1-P2 ) 88.8(3); C40-Ir1-P1
) 89.4(3); C37-Ir1-P2 ) 90.4(3); C37-Ir1-P1 ) 90.3(3); O3-
C40-Ir1 ) 106.6(6); C39-O3-C40 ) 113.7(7); O2-C39-O3 )
125.9(9); C39-O2-Ir1 ) 114.3(6).
Resu lts a n d Discu ssion
Acetatoiridium complexes [Ir(R)(η2-O2CCH3)(CO)-
(PPh3)2]OTf (2, R ) CH3 (a ), CH2Ph (b)) react with HCt
CH in the presence of R′OH and with HCtCCH2CH2OH
to produce acyliridium-alkoxycarbenes [Ir(dC(OR′)CH3)-
(C(dO)R)(η2-O2CCH3)(PPh3)2]OTf (3, R ) CH3, CH2Ph,
R′ ) CH3, CH2CH3) and [Ir(dCOCH2CH2CH2)(C(dO)R)-
(η2-O2CCH3)(PPh3)2]OTf (4, R ) CH3), respectively
(Scheme 1). Reactions of transition metals with terminal
alkynes in the presence of alcohols have provided
synthetic access to various Fischer-type carbenes7 in-
cluding some iridium-alkoxycarbenes.3e,f,4b,8 It is inter-
esting to see that complexes 2 undergo the migra-
tion of the alkyl (R) ligand to the neighboring CO ligand
to provide a vacant coordination site for the newly
formed carbene ligand (Scheme 1), while related
iridium-alkoxycarbenes ([IrCl(CH3)(dC(OCH3)CH3)(CO)-
evident by singlets due to Ir-C(dO)CH3 (δ 1.65 (3a ), 1.72
(3b)) and Ir-C(dO)CH2Ph (δ 3.67 (3c), 3.76 (3d )) and
triplets due to Ir-C(dO)CH3 (ca. δ 198 (3a , 3b)) and Ir-
C(dO)CH2Ph (ca. δ 195 (3c, 3d )) in the 1H and 13C NMR
1
spectra of 3. The H NMR spectrum of 5 shows signals
at δ 5.62 and 4.70 due to the methenyl hydrogens (Ir-
(PMePh2)2]PF6 and [Ir(dCOCH2CH2CH2)Cl(CH3)(CO)-
(PMePh2)2]PF6) maintain both methyl and CO ligands.8
In the absence of an alcohol, the interesting iridacycle
containing a vinyl acetate (-C(dCH2)OC(CH3)O-) ligand
OC(CH3)OC(dCH2)), and the crystal structure of 5
shows the five-member ring and vinyl substituent of the
ring being virtually planar (Figure 1).
Deuterium labeling experiments have been carried
out to obtain more information on the formation of the
acyliridium-alkoxycarbenes 3. Formation of d3 isoto-
pomers [Ir(dC(OR′)CD3)(C(dO)CH3)(η2-O2CCH3)(PPh3)2]-
OTf (3-d 3, R′ ) CH3 (a ), CH2CH3 (b )) and [Ir(d
C(OR′)CH3)(C(dO)CD3)(η2-O2CCH3)(PPh3)2]OTf (3-d 3′,
R′ ) CH3 (a ), CH2CH3 (b)) in eqs 1 and 2 strongly
suggests that the methyl group of IrdC(OR′)CD3 is
originated from HCtCH and R′OD (eq 1) and the acyl
group of 3 is formed by alkyl (R) ligand migration to
the CO ligand (CO insertion into Ir-R bond) (eq 2).
[Ir(OC(CH3)OC(dCH2))(CH3)(CO)(PPh3)2]OTf (5) is ob-
tained from the reaction of 2a with HCtCH (Scheme
1). 1,1-Insertion of an alkyne to a metal-oxygen bond
has been reported for ruthenium and osmium complexes
to produce new M-O-C bonds.9
Complexes 2, 3, 4, and 5 have been unambiguously
1
characterized by spectral (1H, 13C, 31P NMR, H, 13C-
2D HETCOR, and IR) and elemental analysis data, and
crystal structure determination was performed by X-ray
diffraction data analysis for 5 (see Figure 1 and Experi-
mental Section). Complexes 3 and 4 exhibit character-
istic low-field resonances (13C NMR: δ 261.0-265.4) for
R-carbons of the carbene ligands (IrdC(OR′)CH3 and Ir-
(dCOCH2CH2CH2)).3e,f,4b,8,10 Acyl moieties of 3 are
(7) (a) Semmelhack, M. F.; Lindenschmidt, A.; Ho, D. Organome-
tallics 2001, 20, 4114. (b) Hansen, H. D.; Nelson, J . H. Organometallics
2000, 19, 4740. (c) Tenorio, M. A. J .; Tenorio, M. J .; Puerta, M. C.;
Valerga, P. Organometallics 1997, 16, 5528. (d) Sˇteˇpnicˇka, P.; Gyepes,
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Dixneuf, P. H. Organometallics 1991, 10, 2768.
(8) Clark, H. C.; Manzer, L. E. J . Organomet. Chem. 1973, 47, C17.
(9) (a) Sanford, M. S.; Valdez, M. R.; Grubbs, R. H. Organometallics
2001, 20, 5455. (b) Esteruelas, M. A.; Lahoz, F. J .; Lo´pez, A. M.; On˜ate,
E.; Oro, L. A. Organometallics 1994, 13, 1669. (c) Daniel, T.; Mahr,
N.; Braun, T.; Werner, H. Organometallics 1993, 12, 1475.

Acyliridium-Alkoxycarbenes
Sch em e 2
Organometallics, Vol. 22, No. 16, 2003 3241
the acetato ligand on the oxophilic R-carbon (M ) C )
CH2) of vinylidene intermediate B in the absence of an
alcohol (R′OH).
Alkoxycarbene complex 3a slowly changes to 2a to
give CH3COCH3 at 50 °C in CHCl3 solution (eq 3). This
decomposition of 3a seems to occur via alkyl (CH3)
migration from the alkoxycarbene group to the metal
to give the bis(acyl)(methyl)iridium E followed by reduc-
tive elimination of CH3COCH3 and migration of the CH3
group of the acyl ligand (-COCH3) to the metal (CO
deinsertion). It is well known that metal-alkoxycarbenes
(M(dC(OR′)CH2R) decompose to give (acyl)(alkyl)metal
(M(R′)(C(dO)CH2R)) by alkyl group migration to a
metal.13
These results lead us to suggest the mechanism
involving the attack of R′OD on the R-carbon of the
vinylidene ligand as shown in Scheme 2. Not only have
metal-vinylidenes (M ) CdCHR) been frequently ob-
served and suggested in reactions of metals with
terminal alkynes (RCtCH)7b,11 but also their R-carbon
(M ) C ) CHR) is well known to be so electrophilic as
to be attacked by nucleophiles.7a-c,12 It seems quite
reasonable to suggest that the vinylidene ligand is trans
to the CH3 ligand in the intermediate B since the crystal
structure of 5 (Figure 1) shows that HCtCH is inserted
into the Ir-O bond trans to the CH3 ligand of 2a . The
nucleophilic attack of R′OH(D) on the R-carbon (M ) C
) CH2) of B would give the alkoxycarbene complex C-d 3.
The H/D exchange between the vinylidene hydrogens
of B and deuterium of R′OD to give IrdCdCD2 may
occur before the formation of C-d 3 since the H/D
exchange is well known for reactions of metal-vi-
nylidenes with D2O and ROD.12a,c Then the complex
C-d 3 may undergo intramolecular rearrangement (CH3-
(D3) ligand migration to the carbon of the CO ligand) to
give acyl complex 3-d 3, which seems to be favored by
the chelation of the bidentate η2-acetato group.
An intermolecular alkyl group migration is also
observed from the alkoxycarbene ligand of 3a to a
nucleophile such as PPh3 in solution. cis-Bis(acyl)-
iridium(III) complex Ir(C(dO)CH3)2(η2-O2CCH3)(PPh3)2
(6) is obtained presumably from the nucleophilic attack
of PPh3 on the methyl carbon of the methoxy group of
the carbene ligand or by the transfer of the methyl group
of intermediate E (see eq 3) from the metal to PPh3 (eq
4).
A nucleophilic attack at the sp3 carbon-oxygen bond
of the alkoxycarbene ligands has been less commonly
observed,14 while many alkoxycarbene ligands are at-
tacked by nucleophiles at the carbene carbon.15
Alkyl group transfer is also observed in reactions of
1 with PPh3 to give [RPPh3]OTf (R ) CH3, CH2Ph) and
[Ir(CO)(PPh3)3]OTf 16 but never observed with aceta-
toiridium 2. The transfer of an alkyl ligand from a
transition metal to PPh3 is very rare, while alkyl group
transfer reactions from a main-group metal to a transi-
tion metal and between two transition metals are
ubiquitous.17
Acyliridium-alkoxycarbene 4 is obtained presumably
via the intramolecular nucleophilic attack of the pen-
dant hydroxyl group on the R-carbon of the vinylidene
ligand (M ) C ) CHCH2CH2OH) of B, as suggested in
the previously reported iridium carbenes3e,f,4b,8 and the
following CH3 ligand migration to the carbon of CO
ligand as suggested above for the formation of 3.
Formation of iridacycle 5 may be also understood by
the intramolecular nucleophilic attack of the oxygen of
In summary, we have been able to isolate acyliridium-
alkoxycarbenes and an interesting iridacycle containing
a vinyl acetate (-C(dCH2)OC(CH3)O-) ligand from
reactions of alkynes by introducing an ancillary acetato
ligand to the “Ir(CO)(PPh3)2” moiety and observe the
(10) (a) Luecke, H. F.; Bergman, R. G. J . Am. Chem. Soc. 1998, 120,
11008. (b) Luecke, H. F.; Arndtsen, B. A.; Burger, P.; Bergman, R. G.
J . Am. Chem. Soc. 1996, 118, 2517.
(11) (a) Cadierno, V.; Gamasa, M. P.; Gimeno, J . Organometallics
1999, 18, 2821. (b) Bustelo, E.; Tenorio, M. J .; Puerta, M. C.; Valerga,
P. Organometallics 1999, 18, 4563. (c) de los R´ıos, I.; Tenorio, M. J .;
Puerta, M. C.; Valerga, P. J . Am. Chem. Soc. 1997, 119, 6529. (d)
Slugovc, C.; Mereiter, K.; Schmid, R.; Kirchner, K. J . Am. Chem. Soc.
1998, 120, 6175. (e) Huang, D.; Oliva´n, M.; Huffman, J . C.; Eisenstein,
O.; Caulton, K. G. Organometallics 1998, 17, 4700. (f) Bianchini, C.;
Innocenti, P.; Peruzzini, M.; Romerosa, A.; Zanobini, F. Organometal-
lics 1996, 15, 272.
(12) (a) Buil, M. L.; Esteruelas, M. A.; Lo´pez, A. M.; On˜ate, E.
Organometallics 1997, 16, 3169. (b) Bianchini, C.; Casares, J . A.;
Peruzzini, M.; Romerosa, A.; Zanobini, F. J . Am. Chem. Soc. 1996, 118,
4585. (c) Bianchini, C.; Marchi, A.; Marvelli, L.; Peruzzini, M.;
Romerosa, A.; Rossi, R. Organometallics 1996, 15, 3804.
(13) Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J . W. J . Am. Chem.
Soc. 1995, 117, 5503.
(14) (a) Toomey, L. M.; Atwood, J . D. Organometallics 1997, 16, 490.
(b) Fong, R. H.; Lin, C.-H.; Idmoumaz, H.; Hersh, W. H. Organome-
tallics 1993, 12, 503. (c) Cutler, A. R. J . Am. Chem. Soc. 1979, 101,
604. (d) O’Connor, J . M.; Pu, L.; Rheingold, A. L. Organometallics 1988,
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(15) (a) Fischer, H. Mechanistic Aspects of Carbene Complex Reac-
tions. In Transition Metal Carbene Complexes; Seyferth, D., Ed.; Verlag
Chemie: Deerfield Beach, FL, 1983; pp 248-259. (b) Cardin, D. J .;
Cetinkaya, B.; Lappert, M. F. Chem. Rev. 1972, 72, 545. (c) Block, T.
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3242 Organometallics, Vol. 22, No. 16, 2003
Chin et al.
intramolecular and intermolecular transfer of the alkyl
(R′) group of alkoxycarbenes (IrdC(OR′)CH3).
and 128.3 (both s, CH carbons of Ir-CH2C6H5), 134.0 (t),
132.8 (s), 129.5 (t), and 123.6 (t) (Ir-P(C6H5)3), 22.6 (s,
Ir-η2-O2CCH3), 9.2 (br s, Ir-CH2C6H5). 31P{1H} NMR
(81.0 MHz, CDCl3): δ 11.25 (s, Ir-PPh3). IR (KBr, cm-1):
2038 (s, νCtO), 1638 (s, νCdO), 1273, 1098, and 1031
(s, due to uncoordinated OTf-). Anal. Calcd for IrP2-
O6S1F3C47H40: C, 54.07; H, 3.86. Found: C, 54.13; H,
3.90.
[Ir (CD3)(η2-O2CCH3)(CO)(P P h 3)2]OTf (2a -d 3). H
NMR spectrum of 2a -d 3 shows all the signals for 2a
except the disappearance of the triplet signal at δ 1.24
due to Ir-CD3.
Exp er im en ta l Section
Gen er a l In for m a tion . A standard vacuum system
and Schlenk type glassware were used in most of the
experimental procedures in handling metal compounds,
although most of the compounds seem to be stable
enough to handle without much precautions in air.
CH3OD, CH3CH2OD, and CD3I were purchased from
Aldrich. [Ir(OTf)(R)(OH2)(CO)(PPh3)2]OTf (1, R ) CH3
(a ), CH2Ph (b), CD3 (a -d 3)) were prepared by the
literature method6 using CH3I, PhCH2Br, and CD3I,
respectively.
NMR spectra were recorded on either a Varian
Gemini 200, 300, or 500 spectrometer (1H, 300 or 500
MHz; 13C, 126 MHz; 31P, 81.0 MHz). IR spectra were
obtained on a Nicolet 205 spectrophotometer. Elemental
analyses were carried out by a Carlo Erba EA 1108
CHNS-O analyzer at Organic Chemistry Research
Center, Sogang University. Gas chromatography/mass
spectra were measured with a Hewlett-Packard HP
5890A VG-trio 2000 at Korea Research Institute of
Chemical Technology.
P r ep a r a tion of [Ir (R)(η2-O2CCH3)(CO)(P P h 3)2]-
OTf (2, R ) CH3 (a ), CH2P h (b), CD3 (a -d 3)). These
complexes were prepared in the same manner as
described below for 2a . The reaction mixture of 1a (0.1
g, 0.09 mmol) and CH3COOH (0.10 mL, 1.75 mmol) in
CHCl3 (25 mL) was stirred at room temperature for 5 h
before excess CH3COOH was removed by washing with
H2O (3 × 10 mL). Addition of n-pentane (20 mL) to the
CHCl3 solution resulted in white microcrystals of 2a ,
which were collected by filtration, washed with n-
pentane (3 × 20 mL), and dried under vacuum. The
yield was 0.088 g and 98% based on [Ir(CH3)(η2-O2-
CCH3)(CO)(PPh3)2]OTf (2a ).
[Ir (CH3)(η2-O2CCH3)(CO)(P P h 3)2]OTf (2a). 1H NMR
(500 MHz, CDCl3): δ 1.24 (t, J (H-P) ) 5.0 Hz, Ir-CH3,
3H), 0.39 (s, Ir-η2-O2CCH3, 3H). 13C NMR (126 MHz,
CDCl3): δ 190.4 (s, Ir-η2-O2CCH3), 160.2 (t, J (C-P) )
8.5 Hz, Ir-CO), 134.0 (t), 132.7 (s), 129.4 (t), and 123.3
(t) (Ir-P(C6H5)3), 22.9 (s, Ir-η2-O2CCH3), -10.3 (br s, Ir-
CH3). 31P{1H} NMR (81.0 MHz, CDCl3): δ 15.39 (s, Ir-
PPh3 ). IR (KBr, cm-1): 2053 (s, νC≡O), 1638 (s, νCdO),
1268, 1059, and 1032 (s, due to uncoordinated OTf-).
Anal. Calcd for IrP2O6S1F3C41H36: C, 50.88; H, 3.75.
Found: C, 50.84; H, 3.70.
1
P r ep a r a t ion of [Ir (dC(OR ′)CH 3)(C(dO)R )(η2-
O2CCH3)(P P h 3)2]OTf (3, R ) CH3, R′ ) CH3 (a ), R
) CH3, R′ ) CH2CH3 (b), R ) CH2P h , R′ ) CH3 (c),
R ) CH2P h , R′ ) CH2CH3 (d )), [Ir (dC(OR′)CD3)(C(d
O)CH3)(η2-O2CCH3)(P P h 3)2]OTf (3-d 3, R′ ) CH3 (a ),
CH2CH3 (b)), a n d [Ir (dC(OR′)CH3)(C(dO)CD3)(η2-
O2CCH3)(P P h 3)2]OTf (3-d 3′, R′ ) CH3 (a ), CH2CH3
(b)). Complexes 3-d 3 and 3-d 3′ as well as 3b-d were
prepared in a similar manner as described below for 3a .
A 0.1 g (0.1 mmol) sample of 2a in CH3OH (10 mL) was
stirred under HCtCH (1 atm) at 25 °C for 5 h. The
solvent was evaporated before CHCl3 (10 mL) was
added. A 30 mL portion of n-pentane was added to the
CHCl3 solution to precipitate beige microcrystals of 3a ,
which were collected by filtration, washed with n-
pentane (3 × 10 mL), and dried under vacuum. The
yield was 0.10 g and 97% based on [Ir(dC(OCH3)CH3)-
(C(dO)CH3)(η2-O2CCH3)(PPh3)2]OTf (3a ).
[Ir(dC(OCH3)CH3)(C(dO)CH3)(η2-O2CCH3)(PPh3)2]-
1
OTf (3a ). H NMR (500 MHz, CDCl3): δ 3.78 (s, Ird
C(OCH3)CH3, 3H), 1.65 (s, Ir-C(dO)CH3, 3H), 1.63 (s,
IrdC(OCH3)CH3, 3H), 0.67 (s, Ir-η2-O2CCH3, 3H). 13C
NMR (126 MHz, CDCl3): δ 265.1 (t, J (C-P) ) 5.8 Hz,
IrdC(OCH3)CH3), 197.6 (t, J (C-P) ) 5.0 Hz, Ir-C(dO)-
CH3), 186.3 (s, Ir-η2-O2CCH3), 133.9 (t), 132.3 (s), 129.0
(t), and 125.8 (t) (Ir-P(C6H5)3), 65.6 (s, IrdC(OCH3)CH3),
40.7 (s, Ir(dC(OCH3)CH3), 36.4 (s, Ir-C(dO)CH3), 23.2
(s, Ir-η2-O2CCH3). HETCOR (1H (500 MHz) f 13C (126
MHz)): δ 3.78 f 65.6; 1.65 f 36.4; 1.63 f 40.7; 0.67 f
23.2. 31P{1H} NMR (81.0 MHz, CDCl3): δ 3.92 (s, Ir-
PPh3 ). IR (KBr, cm-1): 1655 (s, νCdO), 1276, 1059, and
1032 (s, due to uncoordinated OTf-). Anal. Calcd for
IrP2O7S1F3C44H42: C, 51.51; H, 4.13. Found: C, 51.57;
H, 4.11.
[Ir (dC(OCH 2CH 3)CH 3)(C(dO)CH 3)(η2-O2CCH 3)-
1
(P P h 3)2]OTf (3b). H NMR (500 MHz, CDCl3): δ 3.87
(q, J (H-H) ) 6.9 Hz, IrdC(OCH2CH3)CH3, 2H), 1.72
(s, Ir-C(dO)CH3, 3H), 1.66 (s, IrdC(OCH2CH3)CH3,
3H), 1.45 (t, J (H-H) ) 6.9 Hz, IrdC(OCH2CH3)CH3,
3H), 0.67 (s, Ir-η2-O2CCH3, 3H). 13C NMR (126 MHz,
CDCl3): δ 263.4 (t, J (C-P) ) 5.8 Hz, IrdC(OCH2CH3)-
CH3), 197.9 (t, J (C-P) ) 5.0 Hz, Ir-C(dO)CH3), 186.2
(s, Ir-η2-O2CCH3), 133.9 (t), 132.2 (s), 128.9 (t), and 125.7
(t) (Ir-P(C6H5)3), 65.6 (s, IrdC(OCH2CH3)CH3), 40.7 (s,
IrdC(OCH2CH3)CH3), 36.4 (s, Ir-C(dO)CH3), 23.0 (s, Ir-
η2-O2CCH3), 13.6 (s, IrdC(OCH2CH3)CH3). 31P{1H}
NMR (81.0 MHz, CDCl3): δ 3.75 (s, Ir-PPh3). IR (KBr,
cm-1): 1656 (s, νCdO), 1276, 1096, and 1032 (s, due to
uncoordinated OTf-). Anal. Calcd for IrP2O7S1-
F3C45H44: C, 51.97; H, 4.26. Found: C, 51.97; H, 4.20.
[Ir (CH2P h )(η2-O2CCH3)(CO)(P P h 3)2]OTf (2b). 1H
NMR (500 MHz, CDCl3): δ 7.00 (t, J (H-H) ) 7.5 Hz)
and 6.27 (d, J (H-H) ) 7.5 Hz) (Ir-CH2C6H5, 5H), 3.67
(t, J (H-P) ) 5.0 Hz, Ir-CH2C6H5, 2H), 0.25 (s, Ir-η2-O2-
CCH3, 3H). 13C NMR (126 MHz, CDCl3): δ 188.8 (s, Ir-
η2-O2CCH3), 159.9 (t, J (C-P) ) 8.9 Hz, Ir-CO), 130.0
(17) (a) Bond, A. D.; Hopkins, A. D.; Rothenberger, A.; Wolf, R.;
Woods, A. D.; Wright, D. S. Organometallics 2001, 20, 4454. (b)
Collman, J . P.; Brauman, J . I.; Madonik, A. M. Organometallics 1986,
5, 215. (c) Bryndza, H. E.; Evitt, E. R.; Bergman, R. G. J . Am. Chem.
Soc. 1980, 102, 4948. (d) Ozawa, F.; Fujimori, M.; Yamamoto, T.;
Yamamoto, A. Organometallics 1986, 5, 2144. (e) Scott, J . D.; Pud-
dephatt, R. J . Organometallics 1983, 2, 1643. (f) Hill, G. S.; Yap, G. P.
A.; Puddephatt, R. J . Organometallics 1999, 18, 1408. (g) Ram, M. S.;
Riordan, C. G.; Yap, G. P. A.; Liable-Sands, L.; Rheingold, A. L.;
Marchaj, A.; Norton, J . R. J . Am. Chem. Soc. 1997, 119, 1648. (h)
Canty, A. J .; J in, H.; Roberts, A. S.; Skelton, B. W.; White, A. H.
Organometallics 1996, 15, 5713.
[Ir (dC(OCH 3)CH 3)(C(dO)CH 2P h )(η2-O2CCH 3)-
1
(P P h 3)2]OTf (3c). H NMR (500 MHz, CDCl3): δ 6.97

Acyliridium-Alkoxycarbenes
Organometallics, Vol. 22, No. 16, 2003 3243
(t, J (H-H) ) 7.5 Hz), 6.86 (t, J (H-H) ) 7.5 Hz) and
5.51 (d, J (H-H) ) 7.5 Hz) (Ir-C(dO)CH2C6H5, 5H),
3.69 (s, IrdC(OCH3)CH3, 3H), 3.67 (s, Ir-C(dO)CH2C6H5,
2H), 1.55 (s, IrdC(OCH3)CH3, 3H), 0.69 (s, Ir-η2-O2-
CCH3, 3H). 13C NMR (126 MHz, CDCl3): δ 265.4 (t,
J (C-P) ) 6.3 Hz, IrdC(OCH3)CH3), 194.5 (t, J (C-P) )
5.0 Hz, Ir-C(dO)CH2C6H5), 186.6 (s, Ir-η2-O2CCH3),
134.0 (t), 132.4 (s), 129.2 (t), and 125.8 (t) (Ir-P(C6H5)3),
129.0, 127.5, and 126.1 (s, CH carbons of Ir-C(dO)-
CH2C6H5), 65.8 (s, IrdC(OCH3)CH3), 56.0 (s, Ir-C(dO)-
CH2C6H5), 40.6 (s, IrdC(OCH3)CH3), 23.5 (s, Ir-η2-
O2CCH3). HETCOR (1H (500 MHz) f 13C (126 MHz)):
δ 3.69 f 65.8; 3.67 f 56.0; 1.55 f 40.6; 0.69 f 23.5.
31P{1H} NMR (81.0 MHz, CDCl3): δ 3.40 (s, Ir-PPh3).
IR (KBr, cm-1): 1665 (s, νCdO), 1273, 1095, and 1031
(s, due to uncoordinated OTf-). Anal. Calcd for IrP2-
O7S1F3C50H46: C, 49.03; H, 3.83. Found: C, 49.05; H,
3.85.
0.65 (s, η2-O2CCH3, 3H). 13C NMR (126 MHz, CDCl3):
δ 261.0 (t, J (C-P) ) 6.4 Hz, IrdCOCH2CH2CH2), 198.6
(t, J (C-P) ) 5.4 Hz, Ir-C(dO)CH3), 187.1 (s, Ir-η2-
O2CCH3),87.6(s,IrdCOCH2CH2CH2),56.3(s,IrdCOCH2CH2C-
H2), 36.0 (s Ir-C(dO)CH3,), 23.2 (s, η2-O2CCH3), 20.8 (s,
IrdCOCH2CH2CH2), 134.3, 132.5 129.3, and 125.8 (Ir-
P(C6H5)3). HETCOR (1H (500 MHz) f 13C (126 MHz)):
δ 4.36 f 87.6; 2.48 f 56.3; 1.70 f 36.0; 1.08 f 20.8;
0.65 f 23.2. 31P{1H} NMR (81 MHz, CDCl3): δ 4.85 (s,
PPh3). IR (KBr, cm-1): 1651 (s, νCdO), 1273, 1095, and
1031 (s, due to uncoordinated OTf-). Anal. Calcd for
IrP2O7S1F3C45H42: C, 52.07; H, 4.08. Found: C, 52.35;
H, 3.89.
P r epar ation of [Ir (OC(CH3)OC(dCH2))(CH3)(CO)-
(P P h 3)2]OTf (5). A solution of 2a (0.1 g, 0.1 mmol) in
CHCl3 (10 mL) was stirred under HCtCH (1 atm) at
25 °C for 48 h before n-pentane (30 mL) was added to
precipitate beige microcrystals, which were collected by
filtration, washed with n-pentane (3 × 10 mL), and
dried under vacuum. The yield was 0.093 g and 96%
[Ir (dC(OCH2CH3)CH3)(C(dO)CH2P h )(η2-O2CCH3)-
1
(P P h 3)2]OTf (3d ). H NMR (500 MHz, CDCl3): δ 7.04
(t, J (H-H) ) 7.5 Hz), 6.93 (t, J (H-H) ) 7.5 Hz), and
5.58 (d, J (H-H) ) 7.5 Hz) (Ir-C(dO)CH2C6H5, 5H), 3.80
(q, J (H-H) ) 7.0 Hz, IrdC(OCH2CH3)CH3, 2H), 3.76
(s, Ir-C(dO)CH2C6H5, 2H), 1.68 (s, IrdC(OCH2CH3)CH3,
3H), 1.40 (t, J (H-H) ) 7.0 Hz, IrdC(OCH2CH3)CH3,
3H), 0.74 (s, Ir-η2-O2CCH3, 3H). 13C NMR (126 MHz,
CDCl3): δ 263.6 (t, J (C-P) ) 6.9 Hz, IrdC(OCH2CH3)-
CH3), 194.5 (t, J (C-P) ) 6.8 Hz, Ir-C(dO)CH2C6H5),
186.7 (s, Ir-η2-O2CCH3), 128.9, 127.5, and 126.1 (s, CH
carbons of Ir-CH2C6H5), 76.7 (s, IrdC(OCH2CH3)CH3),
56.0 (s, Ir-C(dO)CH2C6H5), 40.8 (s, IrdC(OCH2CH3)-
CH3), 23.4 (s, Ir-η2-O2CCH3), 13.7 (s, IrdC(OCH2CH3)-
CH3), 134.0 (t), 132.4 (s), 129.1 (t) (Ir-P(C6H5)3). 31P{1H}
NMR (81.0 MHz, CDCl3): δ 3.38 (s, Ir-PPh3). IR (KBr,
cm-1): 1665 (s, νCdO), 1272, 1095, and 1031 (s, due to
based on [Ir(OC(CH3)OC(dCH2))(CH3)(CO)(PPh3)2]OTf
1
(5). H NMR (500 MHz, CDCl3): δ 5.62 (m) and 4.70
(m) (Ir(OC(CH3)OC(dCH2)), 2H), 1.10 (s, Ir(OC(CH3)-
OC(dCH2)), 3H), 0.50 (t, J (H-P) ) 5.5 Hz, Ir-CH3, 3H).
13C NMR (126 MHz, CDCl3): δ 185.2 (s, Ir(OC(CH3)-
OC(dCH2))), 172.7 (t, J (C-P) ) 9.1 Hz, Ir-CO), 165.0
(t, J (C-P) ) 9.1 Hz, Ir(OC(CH3)OC(dCH2))), 116.2 (s,
(Ir(OC(CH3)OC(dCH2))), 15.9 (s, (Ir(OC(CH3)OC-
(dCH2))), -11.3 (t, J (C-P) ) 5.7 Hz, Ir-CH3). HETCOR
(1H (500 MHz) f 13C (126 MHz)): δ 5.62, 4.70 f 116.2;
1.10 f -11.3. 31P{1H} NMR (81.0 MHz, CDCl3): δ 4.93
(s, Ir-PPh3). IR (KBr, cm-1): 2028 (s, νCtO), 1600 and
1576 (s, νCdO), 1270, 1150, and 1031 (s, due to uncoor-
dinated OTf-). Anal. Calcd for IrP2O6S1F3C43H38: C,
49.57; H, 3.68. Found: C, 52.45; H, 3.89.
uncoordinated OTf-). Anal. Calcd for
IrP2-
O7S1F3C51H48: C, 54.88; H, 4.33. Found: C, 54.92; H,
4.38.
[Ir (dC(OR′)CD3)(C(dO)CH3)(η2-O2CCH3)(P P h 3)2]-
OTf (3-d 3, R′ ) CH3 (a ), CH2CH3 (b)). 1H NMR spectra
of 3-d 3 show all the signals for 3 except the disappear-
ance of one singlet at δ 1.63 (3a -d 3) and 1.66 (3b-d 3)
due to IrdC(OCH3)CD3 and IrdC(OCH2CH3)CD3, re-
spectively.
Decom p osition of 3a a t Eleva ted Tem p er a tu r e.
A solution of 3a (0.1 g, 0.1 mmol) in CHCl3 (10 mL) was
stirred at 50 °C for 24 h before distillation under
vacuum to collect acetone in the cold trap of a dry ice/
isopropyl alcohol bath. Acetone was identified by 1H
NMR and GC/MS. To the reduced reaction solution was
added CHCl3 (5 mL) before n-pentane (30 mL) was
added to precipitate beige microcrystals of 2a , which
were collected by filtration, washed with n-pentane (3
× 10 mL), and dried under vacuum.
[Ir (dC(OR′)CH3)(C(dO)CD3)(η2-O2CCH3)(P P h 3)2]-
OTf (3-d 3′, R′ ) CH3 (a ), CH2CH3 (b)). 1H NMR
spectra of 3-d 3′ show all the signals for 3 except the
disappearance of one singlet at δ 1.65 (3a -d 3′) and 1.72
(3b-d 3′) due to Ir-C(dO)CD3.
[Ir (dCOCH 2CH 2CH 2)(C(dO)CH 3)(η2-O2CCH 3)-
(P P h 3)2]OTf (4). A CHCl3 (10 mL) solution of 2a (0.1
g, 0.1 mmol) and HCtCCH2CH2OH (0.01 mL, 0.14
mmol) was stirred at room temperature for 1 h before
n-pentane (20 mL) was added to precipitate beige
microcrystals of 4, which were collected by filtration,
washed with n-pentane (3 × 10 mL), and dried under
vacuum. The yield was 0.096 g and 95% based on
Rea ction of 3a w ith P P h 3: F or m a tion of Ir (C-
(dO)CH3)2(η2-O2CCH3)(P P h 3)2 (6) a n d [CH3P P h 3]-
OTf. To solution of 3a (0.10 g, 0.10 mmol) in CHCl3 (10
mL) was added PPh3 (0.05 g, 0.19 mmol), and the
reaction mixture was stirred at 25 °C under N2 for 2
days before the [CH3PPh3]OTf was removed by extrac-
tion with H2O. Addition of n-pentane (30 mL) resulted
in precipitation of beige microcrystals, which were
collected by filtration, washed with cold n-pentane (3
× 10 mL), and dried under vacuum. The yield was 0.083
g and 96% based on Ir(C(dO)CH3)2(η2-O2CCH3)(PPh3)2
[Ir(dCOCH2CH2CH2)(C(dO)CH3)(η2-O2CCH3)(PPh3)2]-
OTf (4). 1H NMR (500 MHz, CDCl3): δ 4.36 (t, J (H-H)
) 7.5 Hz, IrdCOCH2CH2CH2, 2H), 2.48 (t, J (H-H) )
7.5 Hz, IrdCOCH2CH2CH2, 2H), 1.70 (s, Ir-C(dO)CH3,
3H), 1.08 (q, J (H-H) ) 7.5 Hz, IrdCOCH2CH2CH2, 2H),
1
(6). H NMR (500 MHz, CDCl3): δ 1.78 (s, Ir-C(dO)-
CH3, 6H), 0.64 (s, Ir-η2-O2CCH3, 3H). 13C NMR (126

3244 Organometallics, Vol. 22, No. 16, 2003
Chin et al.
Ta ble 1. Deta ils of Cr ysta llogr a p h ic Da ta
Collection for 5
MHz, CDCl3): δ 206.2 (t, J (C-P) ) 6.2 Hz, Ir-C(dO)-
CH3), 182.2 (s, Ir-η2-O2CCH3), 39.4 (s, Ir-C(dO)CH3),
23.0 (s, Ir-η2-O2CCH3). HETCOR (1H (500 MHz) f 13C
(126 MHz)): δ 1.78 f 39.4; 0.64 f 23.0. 31P{1H} NMR
(81.0 MHz, CDCl3): δ 7.11 (s, Ir-PPh3). IR (KBr, cm-1):
1656 (s, vCdO), 1622 (s, vCdO). Anal. Calcd for
IrP2O4C42H39: C, 58.53; H, 4.56. Found: C, 58.59; H,
4.61.
chemical formula
fw
C43H38F3IrO6P2S
993.99
temp, K
cryst dimens, mm
cryst syst
space group
color of cryst
a, Å
173(2)
0.37 × 0.30 × 0.10
monoclinic
P21/n
colorless
16.068(5)
12.811(5)
24.067(5)
90.000(5)
90.092(5)
90.000(5)
4954(3)
1
[CH3P P h 3]OTf. H NMR (300 MHz, CDCl3): δ 2.96
b, Å
c, Å
(d, J (H-P) ) 13.5 Hz, [CH3PPh3]OTf, 3H). 13C NMR
(126 MHz, CDCl3): δ 9.42 (d, J (C-P) ) 58.8 Hz, [CH3-
PPh3]OTf ), 135.5, 133.3, 130.8, 119.8 (P(C6H5)3). 31P-
{1H} NMR (81.0 MHz, CDCl3): δ 22.56 (s, [CH3PPh3]-
OTf ). IR (KBr, cm-1): 1264, 1150, and 1032 (br s, due
to uncoordinated triflate).
R, deg
â, deg
γ, deg
V, Å3
Z
F
4
(calc), g cm-1
1.653
3.182
2440
µ, mm-1
X-r a y Str u ctu r e Deter m in a tion of [Ir (OC(CH 3)-
F(000)
radiation
wavelength
θ range, deg
hkl range
Mo ΚR
OC(dCH2))(CH3)(CO)(P P h 3)2]OTf (5). Crystals of 5
were grown by slow evaporation from CHCl3 solution.
Preliminary examination and data collection were per-
formed using a Bruker SMART CCD detector single-
crystal X-ray diffractometer using a graphite-monochro-
mated Mo KR radiation (λ ) 0.71073 Å) source equipped
with a sealed tube X-ray source at -100 °C for 5.
Preliminary unit cell constants were determined with
a set of 45 narrow frame (0.3 in ω) scans. A data set
collected consists of 1286 frames of intensity data
collected with a frame width of 0.3 in ω and counting
time of 10 s/ frame at a crystal to detector distance of
5.0 cm. The double pass method of scanning was used
to exclude any noise. The collected frames were inte-
grated using an orientation matrix determined from the
narrow frame scans. SMART and SAINT software
packages (Bruker Analytical X-ray, Madison, WI, 1997)
were used for data collection and data integration.
Analysis of the integrated data did not show any decay.
Final cell constants were determined by a global refine-
ment of 8170 reflections (θ < 28.4). Collected data were
corrected for absorbance using SADABS based upon the
Laue symmetry using equivalent reflections. Crystal
data and intensity data collection parameters are listed
in Table 1. Structure solution and refinement of the
structure were carried out using the SHELXTL-PLUS
(5.03) software package (Sheldrick, G. M., Siemens
Analytical X-ray Division, Madison, WI, 1997). The
structure was solved by direct methods and refined
successfully in the space group P21/n. Full matrix least-
squares refinement was carried out by minimizing
0.71069
1.52-28.37
-20 e h e 21
-14 e k e 17
-32 e l e 19
29 866
no. of reflns
no. of independent reflns
no. of obs (|Fo| > 2σFo) data
no. of params
11 724
8170
635
π and ω scan
0.0640
0.1487
1.058
scan type
a
R1
a
wR2
GOF
R1 ) [∑|Fo| - |Fc|/|Fo|]. wR2 ) [∑w(Fo - Fc2)2/∑w(Fo
) ] ,
a
2
2
2 0.5
2
weighting scheme w ) 1/[σ2Fo + (0.0621P)2 + 34.5562P], where
2
P ) (Fo + 2Fc2)/3.
using appropriate riding model. Details of crystal-
lographic data collection are listed in Table 1. Bond
distances and angles, positional and thermal param-
eters, and anisotropic thermal parameters have been
included in the tables of Supporting Information.
Ack n ow led gm en t. The authors wish to thank the
Korea Research Foundation (KRF) for their financial
support of this study through the Basic Science Re-
search Institute Program (Grant No. 2000-015-DP0224).
Su p p or tin g In for m a tion Ava ila ble: Tables of bond
distances and angles, positional and thermal parameters, and
anisotropic thermal parameters for complex 5 in CIF format
and figures giving 1H NMR (for 2a , 3a , 3c, 4, 5, and 6), 13C
NMR (for 2a , 3a , 3c, 4, 5, and 6), and 1H, 13C-2D HETCOR
(for 3a , 3c, 4, 5, and 6) data. This material is available free of
charge via the Internet at http://pubs.acs.org.
2
2 2
(Fo - Fc ) . The non-hydrogen atoms were refined
anisotropically, and the hydrogen atoms were treated
OM0302746