Phosphorus-carbon bond formation via reactions of triphenylphosphine with acetylene and pentamethylcyclopentadienyl coordinated to iridium(III)

Article abstract of DOI:10.1016/j.ica.2004.01.001

Phosphorus-carbon bond is formed via: (i) the apparent HCCH insertion into Ir-P bond to produce Ir-CH=CH-PPh₃ group and (ii) the activation of the ring-methyl group of the coordinated Cp* (C₅Me ₅^-) to produce Ir

Full text of DOI:10.1016/j.ica.2004.01.001

Inorganica Chimica Acta 357 (2004) 3064–3070
www.elsevier.com/locate/ica
Phosphorus–carbon bond formation via reactions of
triphenylphosphine with acetylene and
pentamethylcyclopentadienyl coordinated to iridium(III) q
*
*
Chong Shik Chin , Yoonho Kim, Hyungeui Lee
Chemistry Department, Sogang University, Seoul 121-742, Republic of Korea
Received 31 December 2003; accepted 6 January 2004
Available online 6 February 2004
Abstract
Phosphorus–carbon bond is formed via: (i) the apparent HCBCH insertion into Ir–P bond to produce Ir–CH@CH–PPh3 group
and (ii) the activation of the ring-methyl group of the coordinated Cpꢀ (C5Me5ꢁ) to produce Ir(g5-C5Me4CH2–PPh3) group from
reactions of iridium(III)–Cpꢀ complexes, [CpꢀIrL3]nþ (n ¼ 1, 2); Cpꢀ ¼ C5Me5ꢁ; L3 ¼ Cl(PPh3)2 (3), (CH3CN)3 (5). The following
new P–C bond containing iridium(III) complexes have been prepared: [CpꢀIr(–CH@CH–PPh3)Cl(PPh3)]þ (4) from 3 with HCBCH;
[Ir(g5-C5Me4CH2–PPh3)(H)(PPh3)2]2þ (6) from 5 with PPh3; [CpꢀIr(–CH@CH–PPh3)2(PPh3)]2þ (7) from 5 with HCBCH and
PPh3; [Ir(g5-C5Me4CH2–PPh3)(–CH@CH–PPh3)Cl(PPh3)]2þ (8) from [Ir(g5-C5Me4CH2–PPh3)(Cl)(PPh3)2]2þ (6-Cl) with
HCBCH; [Ir(g5-C5Me3(1,3-CH2–PPh3)2(H)(PPh3)2)]3þ (10) from [Ir(g5-C5Me4CH2–PPh3)(NCCH3)2(PPh3)]3þ (9) with PPh3;
[Ir(g5-C5Me4CH2–PPh3)(–CH@CH–PPh3)2(PPh3)]3þ (11) from 9 with HCBCH and PPh3.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: P–C bond formation; Phosphorous ylides; Alkyne insertion into Ir–P bond; Activation of the ring-methyl group of Cpꢀ (Cpꢀ ¼ C5Me5ꢁ);
Iridium(III)
1. Introduction
gated to introduce various functional groups to Cpꢀ so
that one can use these functionalized Cpꢀ ligands to
prepare sterically and electronically more diverse metal
complexes [3]. A variety of groups have been success-
fully introduced to replace the hydrogen of the ring-
methyl of Cpꢀ coordinated to metal [3,4]. No report,
to the best of our knowledge, has been made on P–C
bond formation between the ring-methyl carbon of the
coordinated Cpꢀ and phosphine to give phosphorus
ylides (C5Me4CH2–PR3) via direct reaction of tertiary
phosphine with coordinated Cpꢀ while Ru(g5-C5Me4-
CH2–PPh3) was prepared from reaction of Ru(g5-
Transition metal mediated phosphorus–carbon bond
formation reactions could be more useful ones in syn-
thetic organic chemistry than those in the absence of
designed organometallic complexes since enhanced ste-
reo- and regio-selectivity could be obtained from reac-
tions mediated by those metal complexes. Reactions of
PPh3 and hydrocarbyl groups coordinated to metal have
been known to form P–C bond to give saturated and
unsaturated phosphorus ylides C–PPh3 [1,2].
Activation of the ring-methyl group of Cpꢀ
(Cpꢀ ¼ C5Me5ꢁ) coordinated to metal has been investi-
ꢁ
C5Me4CH2Cl) with PPh3/PF6 [5].
During our investigation on carbon-carbon bond
formation via reactions of alkynes with iridium, we
found that phosphorus–carbon bond is readily obtained
by the apparent insertion of alkynes into the Ir–PR3
bond to produce phosphorus ylide C–PR3, which actu-
ally occurs by the attack of PR3 on the coordinated
alkynes [2]. We recently reported carbon-hetero atom
q Supplementary data associated with this article can be found, in the
online version, at doi:10.1016/j.ica.2004.01.001.
* Corresponding authors. Tel.: +82-2-705-8448 (C.S. Chin), +82-2-
714-5915 (H. Lee); fax: +82-2-701-0967.
E-mail addresses: cschin@sogang.ac.kr (C.S. Chin), hleegood@
sogang.ac.kr (H. Lee).
0020-1693/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2004.01.001

C.S. Chin et al. / Inorganica Chimica Acta 357 (2004) 3064–3070
3065
ꢁ
bond formation via reactions of an g5-Cpꢀ (C5Me5
)
seems to make the transfer of the ring-methyl hydrogen
to the metal to provide a vacant site for the hydrogen to
form the Ir–H bond.
complex of iridium(III) (Eq. (1)) [2c] while somewhat
extensive studies for C–P bond formation have been
done with iridium complexes containing (PPh3)2(CO)
unit [2a,2b,2d,2e]. We now wish to report new P–C bond
formed via reactions of iridium complexes of g5-Cpꢀ,
i.e., reactions of PPh3 with HCBCH and the CH3
groups of Cpꢀ coordinated to iridium(III).
The hydrogen transfer from the ring-methyl group of
Cpꢀ to Ir (Eq. (3)) may occur in the intra-molecular
fashion as shown in Scheme 1 as it is not likely to occur
for the proton once dissociated from the methyl group
to transfer to iridium(III) in its higher oxidation state
while the deprotonation of the Cpꢀ to give the tetram-
ethylfulvene Ir(C5Me4@CH2) intermediate could not be
completely excluded. The presumably weak interaction
between the metal and one of the methyl hydrogen
would become stronger by the nucleophilic attack of
PPh3 on the methyl carbon and the C–H bond would be
eventually cleaved to give Ir–H and C–PPh3 bonds in 6
(Scheme 1).
HCBCH;B
½LnIr–NCCH3ꢂþ
!
½LnIr–CH@CH–Bꢂþ
ð1Þ
–CH3CN
1
2
where Ln ¼ (g3-CH2CHCHPh)(g5-Cpꢀ); B ¼ NEt3 (a),
PPh3 (b), AsPPh3 (c).
2. Results and discussion
PPh3
Reactions of CpꢀIrIIIL3 (L3 ¼ Cl(PPh3)2, (CH3CN)3,
etc.) complexes with PPh3 in the absence and presence of
HCBCH produce new compounds with newly formed
P–C (Ph3P–C) bonds. The formation of 6 (Eq. (3)) is
somewhat surprising while that of 4 (Eq. (2)) is not so
unusual since we recently reported the related com-
plexes, 2 (see Eq. (1)) [2] but the attack of a tertiary
phosphine on the ring-methyl carbon of coordinated
Cpꢀ to form C–PPh3 bond (Eq. (3)) has not been pre-
viously reported.
The apparent insertion of HCBCH into Ir–P bond
(Eq. (2)) is understood, as previously suggested [2,6], by
the following steps: (i) initial dissociation of one PPh3
from 3 to provide a vacant site, (ii) coordination of
HCBCH to the vacant site and (iii) attack of PPh3 on
the carbon of the coordinated HCBCH to form the Ir–
CH@CH–PPh3 moiety. The reaction (Eq. (2)) is signif-
icantly retarded by the excess of PPh3.
Metal complexes of Cpꢀ undergo a variety of reac-
tions in the presence of strong bases for the substitution
of the hydrogen of the ring-methyl group to produce g5-
C5Me4CH2–A (A ¼ PR2, NR2, R, OR, CHO, X and,
etc.) [3–5]. Metal complexes of g4- and g6-tetramethyl-
fulvene (C5Me4@CH2) have been observed and sug-
gested as the intermediates produced by deprotonation
of the ring-methyl group of Cpꢀ in the presence of
strong bases [3–7].
2+
3 PPh3
[Cp*Ir(NCCH3)3]2+
ð3Þ
Ir
H
- 3 CH3CN
Ph3P
PPh3
5
6
The hydride ligand of 6 is readily replaced with
chloro ligand to give 6-Cl [(C5Me4(CH2–
PPh3))Ir(Cl)(PPh3)2]2þ (see Fig. 1 for the crystal struc-
ture of 6-Cl) in chlorinated solvents such as CHCl3 and
PhCH2Cl.
Under the atmosphere of HCBCH, complex 5
surprisingly undergoes the apparent HCBCH insertion
into two Ir–PPh3 bonds to give complex 7 (Eq. (4)).
The formation of 7 (Eq. (4)) is also attributed to the
lability of the CH3CN ligand of 5 being readily
substituted by HCBCH and the nucleophilicity of PR3
attacking on the coordinated HCBCH. Varying
amounts of PPh3 in the reaction mixture of 5 and
PPh3 under 1 atm of HCBCH does not give any
other product than 7.
2+
HC CH, 3 PPh3
[Cp*Ir(NCCH3)3]2+
Ir
PPh3
PPh3
ð4Þ
- 3 CH3CN
5
Ph3P
7
While the reaction of the hydrido complex 6 with
HCBCH gives unidentified complex(es), the chloro
+
HC CH
[Cp*IrCl(PPh3)2]+
Ir Cl
ð2Þ
PPh3
Ph3P
3
PPh3
H
PPh3
4
CH2
H
The activation of the ring-methyl group of Cpꢀ in 3
(Eq. (3)) does not occur from the reaction of 3 with
excess PPh3 in the presence or absence of HCBCH.
Replacing the three ligands, Cl(PPh3)2 of 3 with
(CH3CN)3 makes the ring-methyl group of Cpꢀin 5 re-
active with PPh3. The lability of CH3CN ligand of 5
PPh3
NCCH3
[Ir]
[Ir]
[Ir]
- CH3CN
6
5
[Ir] = [IrL2]2+ (L = CH3CN (5), PPh3 (6))
Scheme 1.

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C.S. Chin et al. / Inorganica Chimica Acta 357 (2004) 3064–3070
PPh3
3+
PPh3
+
2Ag+, 2CH3CN
-AgCl, -AgI
CH3I
- [CH3PPh3]+
ð6Þ
6-Cl
Ir
I
Ir NCCH3
NCCH3
9
Ph3P
Ph3P
Cl
A
C7
P1
C6
PPh3
3+
PPh3
3+
C2
C8
C9
C3
C1
Ph3P
ð7Þ
2 PPh3
- 2 CH3CN
C10
Ir NCCH3
H
Ir
C4
C5
Ph3P
NCCH3
Ph3P
PPh3
Cl9
P3
9
Ir1
10
P2
Another ring-methyl group of the coordinated g5-
C5Me4(CH2–PPh3) in 9 is activated in the reaction of 9
with PPh3 (in the absence of HCBCH) to give the hydr-
ido-1,3-di-ring-methyl group substituted Cpꢀ complex 10
(Eq. (7)). Two different products have been reported from
the double C–H activation of the ring-methyl group of
Cpꢀ coordinated to metal [8–10]. While the double C–H
bond activation occurs at the 1 and 3 ring-methyl groups
of Cpꢀ in the reaction of [(g5-C5Me5)RhBr(l-Br)]2 with
(C6F5)2PCH2CH2–P(C6F5)2 to give [{g5-C5Me4CH2-
C6F4P(C6F5)CH2CH2P(C6F5)2}RhBr]þ [8], the double
ring-metalation at the two neighboring methyl groups
of Cpꢀ has been reported for the reaction of CpꢀTaCl4
with sodium amalgam in the presence of PMe3 to give
the 1,2-di-methyl group substituted Cpꢀcomplex, {g5-
C5Me3-1,2-(CH2)2}Ta(H)2(PMe3)2 [9]. Both 1,2- and
1,3-ring-methyl group activation has been also observed
for the Cpꢀ in [CpꢀRhCl(Ph2PCH@CH2)2]þ from the
reaction with potassium tert-butoxide to give [{g5-
C5Me3-1,2-[CH2CH2CH2P(C6H5)2]2}RhCl]þ and [{g5-
C5Me3-1,2-[CH2CH2CH2P(C6H5)2]2}RhCl]þ [10].
Again, the hydride (Ir–H) of 10 may come from the
ring-methyl group of C5Me4(CH2–PPh3) of 9 as sug-
gested above for the formation of 6 (see Scheme 1).
Complex 9 undergoes the apparent HCBCH inser-
tion reaction into two Ir–PPh3 bonds under the atmo-
sphere of HCBCH in the presence of PPh3 to give 11
(Eq. (8)) that has three C–P bonds (one Ir–CH@C–PPh3
and two Ir(C5Me4–CH2–PPh3)).
Fig. 1. ORTEP drawing of [(g5-C4Me4CH2PPh3)IrCl (PPh3)2](OTf)2
(6-Cl) with 50% thermal ellipsoids probability. Counter-anion (OTf)
and hydrogen atoms are omitted for clarity. Selected bond distances
ꢀ
(A): Ir1–C1 ¼ 2.226(10); Ir1–C2 ¼ 2.278(10); Ir1–C3 ¼ 2.289(11); Ir1–
C4 ¼ 2.258(11); Ir1–C5 ¼ 2.245(10); C1–C2 ¼ 1.471(14); C2–C3 ¼
1.409(15); C3–C4 ¼ 1.429(16); C4–C5 ¼ 1.443(15); C1–C5 ¼ 1.423(14);
C1–C6 ¼ 1.479(15); C2–C7 ¼ 1.494(15); C3–C8 ¼ 1.509(15); C4–C9 ¼
1.494(16); C5–C10 ¼ 1.511(14); P1–C6 ¼ 1.839(10). Selected bond
angles (deg): C1C6P1 ¼ 116.3(7); C6–C1–Ir1 ¼ 127.9(7); C7–C2–
Ir1 ¼ 128.2(7); C8–C3–Ir1 ¼ 133.6(8); C9–C4–Ir1 ¼ 135.0(8); C10–C5–
Ir1 ¼ 132.0(7).
complex 6-Cl ([(C5Me4(CH2–PPh3))Ir(Cl)(PPh3)2]2þ
)
reacts with HCBCH to produce 8 which has both sat-
urated (–CH2–PPh3) and unsaturated (@CH–PPh3)
phosphorus ylide groups (Eq. (5)). The formation of 8
(Eq. (5)) is significantly retarded by the presence of ex-
cess PPh3 in the reaction mixture, which suggests the
dissociation of PPh3 from 6-Cl occurring prior to the
coordination of HCBCH which is then attacked by
PPh3.
2+
PPh3
3+
PPh3
PPh3
3+
HC CH
Ir Cl
PPh3
ð5Þ
6-Cl
2 HC CH, 2 PPh3
-2 CH3CN
ð8Þ
Ir NCCH3
NCCH3
9
Ir
PPh3
Ph3P
Ph3P
Ph3P
PPh3
11
8
We have seen above that introducing labile ligand
such as CH3CN in place of non-labile ligand such as Clꢁ
and PPh3 enhances the reactivity of these iridium com-
plexes investigated in this study especially toward
phosphines and HCBCH to form new P–C bonds. In
order to see further new P–C bond formation, complex 9
containing two CH3CN ligands has been prepared from
reaction of 6-Cl according to Eq. (6).
We have not been successful to prepare complexes
containing more than three C–PPh3 bonds probably due
to the bulkiness of PPh3.
New complexes, 4, 6–11 have been unambiguously
characterized by 1H-, 13C-, 31P NMR, 1H, 13C-2D
HECTOR, IR spectral and elemental analysis data
analysis (see Section 3 for detailed assignments and
Supplementary material), and also by X-ray diffraction

C.S. Chin et al. / Inorganica Chimica Acta 357 (2004) 3064–3070
3067
data analysis for the crystal structure of 6-Cl. Spectral
data analyses are mostly straightforward by comparing
with those of related compounds from our recent studies
as well as others [1,2].
N2 for 10 h at 25 °C and distilled under vacuum to
obtain yellow solid which was recrystallized in chloro-
form/diethyl ether to obtain yellow microcrystals of 6.
1
The yield was 0.68 g and 97% based on 6. H NMR
These newly prepared complexes 4, 6–11 in study are
soluble in polar solvents such as CHCl2, CHCl3and
CH3COCH3, stable in the solid state in air and in so-
lution under N2.
(CDCl3, 500 MHz): d ꢁ15:4 (td, 1H, J (H,Pb) ¼ 28.0 Hz,
J(H,Pa) ¼ 6.3 Hz, Ir–H), 0.73 and 1.50 (both s, 12H,
C5(CH3)4), 3.70 (d, 2H, J(H,Pa) ¼ 11.0 Hz, CH2Pa). 13C
NMR (CDCl3, 126 MHz): d 9.27 and 9.54 (s, C5(CH3)5),
82.5, 101.6 and 104.7 (s, C5(CH3)5), 23.0 (d,
1
J(C,Pa) ¼ 47.0 Hz, CH2Pa). H, 13C-2D HETCOR (1H
3. Experimental
(500 MHz) ! 13C (126 MHz)):
d
0.73 ! 9.27;
1.50 ! 9.54; 3.70 ! 23.0. 31P{1H} NMR (CDCl3, 81
MHz): d 17.4 (t, Pa, J(Pa,Pb) ¼ 9.3 Hz), 6.86 (d, Pb,
J(Pa,Pb) ¼ 9.3 Hz). IR (KBr, cmꢁ1): 1230, 1100 and 1039
(br s, OTf), 2172 (m, Ir–H). Anal. Calc. for
Ir1P3C66H60S2F6O6: C, 56.12; H, 4.28; S, 4.54. Found:
C, 56.13; H, 4.43; S, 4.54%.
3.1. General information
A
standard vacuum system and Schlenk type
glassware were used in handling metal complexes un-
der N2 although most of metal complexes seem to be
stable.
The NMR spectra were recorded on a Varian 300 or
1
500 MHz spectrometer for H and 75 or 126 MHz for
3.2.3.
Synthesis
of
(PPh3)2](OTf)2 (6-Cl)
[Ir(g5-C5Me4CH2–PPh3)Cl-
13C, and 81 MHz for 31P. Infrared spectra were obtained
on a Nicolet 205. Elemental analysis was carried with a
Carlo Erba EA1108 at the Organic Chemistry Center,
Sogang University.
A solution of 6 in CHCl3 was stirred at 25 °C for 30
min under N2 and distilled to obtain yellow microcrys-
tals of 6-Cl. H NMR (CD2Cl2, 500 MHz): d 0.62 and
1
1.11 (both s, 12H, C5(CH3)4), 2.80 (d, 2H, J(H,P) ¼ 11.0
Hz, CH2Pa). 13C NMR (CD2Cl2, 126 MHz): d 11.6 (s,
C5(CH3)5), 82.5, 101.6 and 104.7 (s, C5(CH3)5), 22.5 (d,
3.2. Synthesis
CpꢀIrCl(PPh3)2 (3) [3] and [CpꢀIr(NCMe)3](OTf)2 (5)
[11] were prepared by the literature methods.
1
J(C,Pa) ¼ 49.5 Hz, CH2Pa). H, 13C-2D HETCOR (1H
(500 MHz) ! 13C (126 MHz)): d 0.62, 1.11 ! 11.6;
2.80 ! 22.5. 31P{1H} NMR (CD2Cl2, 81 MHz): d 18.3
(t, Pa, J(Pa,Pb) ¼ 11.6 Hz), -11.7 (d, Pb, J(Pa,Pb) ¼ 11.6
Hz). IR (KBr, cmꢁ1): 1230, 1100 and 1039 (br s, OTf).
Anal. Calc. for Ir1P3C66H59S2F6O6Cl1: C, 54.79; H,
4.11; S, 4.43. Found: C, 54.53; H, 4.03; S, 4.63%.
3.2.1. Synthesis of [CpꢀIr(–CH@CH–PaPh3)Cl(Pb- Ph3)]-
OTf (4)
A solution of 3 (0.10 g, 0.11 mmol) in CH3COCH3
(20 ml) was stirred under HCBCH (1 atm) for 10 hours
at 25 °C before diethyl ether (30 ml) was added to pre-
cipitate beige microcrystals, which were collected, wa-
shed with diethyl ether (3 ꢃ 10 ml) and dried in vacuum.
3.2.4. Synthesis of [CpꢀIr(–CH@CH–PPh3)2(PPh3)]-
(OTf)2 (7)
1
The yield was 0.10 g and 98% based on 4. H NMR
(CDCl3, 500 MHz): d 1.3 (s, 15H, C5(CH3)5), 6.9 (ddd,
1H, J(H,Pa) ¼ 34.0 Hz, J(H,H) ¼ 17.0 Hz, J(H,Pb) ¼ 1.5
Hz, Ir–CH@CH–PPh3), 9.9 (ddd, 1H, J(H,Pa) ¼ 29.0
Hz, J(H,H) ¼ 17.0 Hz, J(H,Pb) ¼ 8.0 Hz, Ir–CH@CH–
PPh3). 13C NMR (CDCl3, 126 MHz): d 8.3 (s,
C5(CH3)5), 95.7 (s, C5(CH3)5), 178.0 (dd, Ir–
CH@CHPPh3, J(C,Pa) ¼ 14.3 Hz, J(C,Pb) ¼ 8.1 Hz),
107.7 (d, Ir–CH@CHPPh3, J(C,Pa) ¼ 71.0 Hz). 1H, 13C-
2D HETCOR (1H (500 MHz) ! 13C (126 MHz)): d 9.9
178.0; 6.9 ! 107.7. 31P NMR (CDCl3, 81 MHz): d 15.0
(d, J(Pa,Pb) ¼ 7.4 Hz), 3.3 (d, J(Pa,Pb) ¼ 7.4 Hz). IR
(KBr, cmꢁ1): 1258, 1140 and 1026 (br. s, OTf). Anal.
Calc. for Ir1P2C49H47F3O3S1Cl1: C, 62.74; H, 5.05; S,
3.42. Found: C, 62.65; H, 4.97; S, 3.34%.
A 0.52 g (2.00 mmol) of PPh3was added to a solution
of 5 (0.37 g, 0.50 mmol) in CH3COCH3 (20 ml) under
HCBCH (1 atm) and the resulting solution was stirred
for 10 h at 50 °C before diethyl ether (30 ml) was added
to precipitate beige microcrystals which were collected,
washed with diethyl ether (3 ꢃ 10 ml) and dried in vac-
uum. The yield was 0.71 g and 97% based on 7. 1H
NMR (CDCl3, 500 MHz): d 1.4 (s, 15H, C5(CH3)5), 6.2
(dd, 2H, J(H,Pa) ¼ 29.5 Hz, J(H,H) ¼ 17.7 Hz, Ir–
CH@CHPPh3), 9.9 (ddd, 2H, J(H,Pa) ¼ 29.4 Hz,
J(H,H) ¼ 17.7 Hz, J(H,Pb) ¼ 4.2 Hz, Ir–CH ¼ CHPPh3).
13C NMR (CDCl3, 126 MHz): d 8.8 (s, C5(CH3)5), 98.3
(s, C5(CH3)5), 176.6 (dd, Ir–CH@CHPPh3), 107.7 (d, Ir–
CH@CHPPh3; J(C,P) ¼ 72.4 Hz). 1H, 13C-2D HET-
COR (1H (500 MHz) ! 13C (126 MHz)): d 9.9 ! 176.6;
6.2 ! 107.7. 31P{1H} NMR (CDCl3, 81 MHz): d 23.0 (d,
J(Pa,Pb) ¼ 2.0 Hz, Ir–CH@CHPaPh3), 8.38 (t,
J(Pb,Pa) ¼ 2.0 Hz, Ir–PbPh3). IR (KBr, cmꢁ1): 1259,
1147 and 1026 (br. s, OTf). Anal. Calc. for
3.2.2. Synthesis of [Ir(g5-C5Me4CH2–PaPh3)(H)-
(PbPh3)2](OTf)2 (6)
A reaction mixture of 5 (0.37 g, 0.50 mmol) and PPh3
(0.52 g, 2.00 mmol) in CH3CN (20 ml) was stirred under

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C.S. Chin et al. / Inorganica Chimica Acta 357 (2004) 3064–3070
Ir1P3C70H64F6S2O6: C, 57.41; H, 4.40; S, 4.38. Found:
C, 57.53; H, 4.49; S, 4.41%.
removed by filtration. The yellow filtrate was distilled
under vacuum to dryness. The yield was 0.66 g and
95% based on 9.
3.3. Synthesis of [Ir(g5-C5Me4CH2–PPh3)(–CH@CH–
PPh3)Cl(PPh3)](OTf)2 (8)
PaPh3
3+
Ir
NCCH3
NCCH3
A solution of 6-Cl (0.72 g, 0.50 mmol) in CH3COCH3
(20 ml) was stirred under HCBCH (1 atm) for 10 h at 25
°C before diethyl ether (30 ml) was added to precipitate
beige microcrystals, which were collected, washed with
diethyl ether (3 ꢃ 10 ml) and dried in vacuum. The yield
was 0.72 g and 98% based on 8.
Ph3Pb
9
1H NMR (CD3COCD3, 300 MHz): d 1.2 (d, 6H,
J(H,Pa) ¼ 2.2 Hz, C5(CH3)4), 1.5 (d, 6H, J(H,Pa) ¼ 2.0
Hz, C5(CH3)4), 2.7 (s, 6H, CH3CN), 4.7 (d, 2H,
2+
J(H,Pa) ¼ 14.2
Hz,
CH2Pa).
31P{1H}
NMR
PaPh3
(CD3COCD3, 81 MHz): d 18.9 (d, J(Pa,Pb) ¼ 0.18 Hz),
7.9 (d, J(Pa,Pb) ¼ 0.18 Hz). IR (KBr, cmꢁ1): 1230, 1100
and 1039 (br s, OTf). Anal. Calc. for
Ir1P2C53H50N2S3F9O9: C, 46.12; H, 3.65; S, 6.97.
Found: C, 46.52; H, 3.74; S, 6.89%.
Ir Cl
PbPh3
Ph3Pc
8
1H NMR (CDCl3, 500 MHz): d 0.48 (d, 3H,
J(H,P) ¼ 2.5 Hz, C5(CH3)4), 0.77 (d, 3H, J(H,P) ¼ 2.0
Hz, C5(CH3)4), 1.57 (d, 3H, J(H,P) ¼ 3.5 Hz, C5(CH3)4),
1.67 (s, 3H, J(H,P) ¼ 2.5 Hz, C5(CH3)4), 3.2 (dd, 1H,
J(H,H0) ¼ 15.5 Hz, J(H,Pa) ¼ 12.0 Hz, CHH0Pa), 3.6
(dd, 1H, J(H,H0) ¼ 15.5 Hz, J(H0,Pa) ¼ 12.0 Hz,
CHH0Pa) 6.9 (ddd, 1H, J(H,Pc) ¼ 32.0 Hz, J(H,H) ¼
17.0 Hz, J(H,Pb) ¼ 1.0 Hz, Ir–CH@CHPaPh3), 10.1
(ddd, 1H, J(H,P) ¼ 28.0 Hz, J(H,H) ¼ 17.0 Hz,
J(H,Pb) ¼ 6.5 Hz, Ir–CH@CHPPh3).13C NMR (CDCl3,
126 MHz): d 7.81, 8.42, 8.51 and 8.80 (s, C5(CH3)5),
75.2, 98.0, 102.1 and 122 (s, C5(CH3)5), 22.0 (d,
J(C,Pa) ¼ 46.0 Hz, CH2Pa), 109.5 (d, Ir–CH@CHPcPh3;
J(C,Pc) ¼ 68.0 Hz), 174.1 (dd, J(C,Pc) ¼ 11.0 Hz,
J(C,Pb) ¼ 9.0 Hz, Ir–CH@CHPcPh3). 1H, 13C-2D
HETCOR (1H (500 MHz) ! 13C (125.7 MHz)): d
0.48 ! 8.51; 0.77 ! 8.80; 1.57 ! 7.81; 1.67 8.42; 3.2,
3.6 ! 22.0; 6.9 ! 109.5; 10.1 ! 174.1. 31P{1H} NMR
(CDCl3, 81 MHz): d 16.2 (d, J(Pa,Pb) ¼ 4.3 Hz), 14.5 (d,
J(Pc,Pb) ¼ 6.7 Hz), 2.1 (dd, J(Pc,Pb) ¼ 6.7 Hz,
J(Pa,Pb) ¼ 4.3 Hz). Anal. Calc. for Ir1P3C68H61F6
S2O6Cl1: C, 55.45; H, 4.17; S, 4.35. Found: C, 55.40; H,
4.01; S, 4.26%.
3.3.2. Synthesis of [C5(CH3)3(CH2PPh3)2Ir(H)-
(PPh3)2](OTf)3 (10)
A reaction mixture of 9 (0.69 g, 0.50 mmol) and PPh3
(0.52 g, 2.0 mmol) in CH3COCH3 (20 ml) was stirred for
1 day under N2 at 25 °C. The filtrate was distilled under
vacuum to obtain pale yellow powders, which were re-
crystallized in CH3Cl/diethyl ether to obtain pale yellow
microcrystals. The yellow filtrate was distilled under
vacuum to dryness. The yield was 0.86 g and 94% based
on 10.
3+
PaPh3
Ph3Pa
Ir
H
Ph3Pb
PbPh3
10
1H NMR (CDCl3, 500 MHz): d ꢁ15:8 (tt, 1H,
J(H,Pb) ¼ 28.0 Hz, J(H,Pa) ¼ 6.30 Hz, Ir–H), 0.56 (s,
3H, 2-CH3 of C5(CH3)3), 1.01 (s, 6H, 4- and 5-CH3 of
C5(CH3)3), 3.60 (t, 2H, J(H,Pa) ¼ 14.6 Hz,
J(H,H0) ¼ 14.6 Hz, CHH0Pa), 3.90 (t, 2H, J(H0,Pa) ¼
14.6 Hz, J(H,H0) ¼ 14.6 Hz, CHH0Pa). 13C NMR
(CDCl3, 126 MHz): d 9.60 (s, 4- and 5-CH3 of
C5(CH3)3), 10.3 (s, 2-CH3 of C5(CH3)3), 88.5 and 104.5
3.3.1. Synthesis of [Ir(g5-C5Me4CH2–PPh3)(PPh3)-
(NCCH3)2](OTf)3 (9)
1
(s, C5(CH3)5), 23.9 (d, J(C,Pa) ¼ 48.4 Hz, CH2Pa). H,
13C-2D HETCOR (1H (500 MHz) ! 13C (126 MHz)): d
0.56 10.3; 1.01 ! 9.60; 3.6 and 3.9 ! 23.9. 31P{1H}
NMR (CDCl3, 81 MHz): d 17.7 (t, J(Pa,Pb) ¼ 5.2 Hz),
2.8 (t, J(Pa,Pb) ¼ 5.2 Hz). IR (KBr, cmꢁ1): 1230, 1100
and 1039 (br s, OTf), 2172 (m, Ir–H). Anal. Calc. for
Ir1P4C85H74F9 S3O9: C, 56.01; H, 4.09; S, 5.28. Found:
C, 56.11; H, 4.12; S, 5.20%.
A reaction mixture of 6-Cl (0.72 g, 0.50 mmol) and
CH3I (0.041 ml, 0.66 mmol) in CH3COCH3 (20 ml)
was stirred for 20 h under N2 at 25 °C before the
solvent was distilled under vacuum to dryness to obtain
red solid. The solid was dissolved in CH3CN (20 ml) of
AgOTf (0.26 g, 1.0 mmol) and the reaction mixture
was stirred for 15 min at 25 °C before white AgCl was

C.S. Chin et al. / Inorganica Chimica Acta 357 (2004) 3064–3070
3069
Table 1
Details of crystallographic data collection for 6-Cl
3.4. Synthesis of [C5(CH3)4CH2PPh3Ir(CH@CHP-
Ph3)2(PPh3)](OTf)3 (11)
Chemical formula
Formula weight
Temperature (K)
Crystal dimensions (mm)
Crystal system
C66H59ClF6IrO6P3S2
1354.06
A solution of 9 (0.69 g, 0.50 mmol) and PPh3 (0.52 g,
2.0 mmol) in CH3COCH3 was stirred for 10 h under
HCBCH (1 atm) at 25 °C. The filtrate was distilled
under vacuum to obtain pale yellow powders which
were recrystallized in CH3Cl/diethyl ether to obtain
yellow microcrystals. The yield was 0.87 g and 93%
based on 11.
293(2)
0.46 ꢃ 0.44 ꢃ 0.20
triclinic
ꢁ
Space group
ꢀ
P1
a (A)
11.483(2)
14.963(3)
23.657(5)
85.964(3)
86.241(3)
84.281(3)
4027.3(14)
3
ꢀ
b (A)
ꢀ
c (A)
a (°)
b (°)
c (°)
3+
PaPh3
3
ꢀ
V (A )
Z (Mg/m3)
q (calc) (g/cmꢁ1
)
1.802
3.132
2181
Ir
PbPh3
l (mmꢁ1
F ð000Þ
)
Ph3Pc
Radiation
Wavelength
Mo Ka
0.71073
51.1
PcPh3
11
2h maximum (°)
hkl range
ꢁ13 6 h 6 13; ꢁ18 6 k 6 18;
ꢁ28 6 l 6 26
30 593
1H NMR (CDCl3, 300 MHz): d 0.8 (d, 6H,
J(H,Pa) ¼ 2.2 Hz, C5(CH3)4), 1.4 (d, 6H, J(H,Pa) ¼ 2.0
Hz, C5(CH3)4), 3.9 (d, 2H, J(H,Pa) ¼ 11.8 Hz, CH2Pa),
6.7 (ddd, 2H, J(H,Pc) ¼ 30.2 Hz, J(H,H) ¼ 17.0 Hz,
J(H,Pb) ¼ 1.0 Hz, Ir–CH@CHPcPh3), 9.7 (ddd, 2H,
J(H,Pc) ¼ 30.2 Hz, J(H,H) ¼ 17.0 Hz, J(H,Pb) ¼ 4.6 Hz,
Ir–CH@CHPcPh3). 31P{1H} NMR (CDCl3, 81 MHz): d
18.2 (d, J(P,P) ¼ 7.3 Hz), 16.7 (d, J(P,P) ¼ 5.6 Hz), 7.1
(dd, J(P,P) ¼ 7.3 Hz, J(P,P) ¼ 5.6 Hz). IR (KBr, cmꢁ1):
1230, 1100 and 1039 (br s, OTf). Anal. Calc. for
Ir1P4C89H78O9S3F9: C, 57.01; H, 4.19; S, 5.13. Found:
C, 57.13; H, 4.18; S, 5.14%.
Number of reflections
Number of unique data
Number of observed
(jFoj > 2rFo) data
Number of parameters
Scan type
14 887
14 887
871
x=2h scan
0.0974
0.2072
1.377
P
R1
wR2
GOF
P
P
2
2 0:5
R1 ¼ ½ jFoj ꢁ jFcj=jFojꢂ, wR2 ¼ ½ wðFo2 ꢁ Fc2Þ = wðFo2Þ ꢂ
.
2
Weighting scheme: w ¼ 1=½r2Fo2 þ ð0:0573PÞ þ 44:3205Pꢂ where
P ¼ ðFoþ2Fc2Þ=3.
3.4.1. X-ray structure determination of [Ir(g5-
C5Me4CH2–PPh3)Cl(PPh3)2](OTf)2 (6-Cl)
4. Conclusion
Crystals of 6-Cl were grown by slow evaporation from
CH2Cl2/n-hexane solution. The crystal evaluation and
data collection were performed on a Bruker CCD dif-
factometer with radiation Mo Ka (k ¼ 0:71073). Pre-
liminary orientation matrix and cell constants were
determined from three series of x-scan at different
starting angles. Each series consisted of 10 frames col-
lected at intervals of 0.3° x-scans with the exposure time
10 s per frame. The structure of this compound was
solved by direct methods from the E-map (SHELXS-TL).
Non-hydrogen atoms were located in an alternating
series of least-squares cycles and difference Fourier
maps. Non-hydrogen atoms were refined with aniso-
tropic displacement coefficients. All hydrogen atoms
were included in the structure factor calculation at
idealized positions and were allowed to ride on the
neighboring atoms with relative isotropic displacement
coefficients. Details of crystallographic data collection
are listed in Table 1. Bond distances and angles, posi-
tional and thermal parameters, and anisotropic thermal
parameters have been included in CIF format of Sup-
plementary material.
Phosporus–carbon bond formation is achieved by the
nucleophilic attack of PPh3 on the carbon of the coor-
dinated HCBCH to iridium(III)-Cpꢀ to produce Ir–
CH@CH–PPh3 groups and on the ring-methyl carbon
of Cpꢀ coordinated to iridium(III) to produce Ir(g5-
C5Me4CH2–PPh3) and Ir(g5-C5Me3(1,3-CH2–PPh3)2)
groups. Replacement of non-labile ligands such as PPh3
and Clꢁ with labile ligand CH3CN provides vacant sites
for: (i) coordination of HCBCH to the metal attracting
the nucleophilic attack of PPh3 on the coordinated
HCBCH to form Ir–CH@CH–PPh3 bond and (ii) for
the hydrogen transferred from the ring-methyl group of
the coordinated Cpꢀ to produce the new Ir(C5Me4CH2–
PPh3) bond.
5. Supplementary material
Crystallopraphic data for the structural analysis have
been deposited with the Cambridge Crystallographic

3070
C.S. Chin et al. / Inorganica Chimica Acta 357 (2004) 3064–3070
Data Center, CCDC No. 227514. Copies of this infor-
mation can be obtained free of charge via
www.ccdc.cam.ac.uk/conts/retrieving.html (or from the
Cambridge Crystallograhpic Data Centre, 12, Union
Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033;
e-mail: deposit@ccdc.cam.ac.uk) and 1H NMR (for 4, 6,
6-Cl, 7, 8, 10 and 11), 13C NMR (for 4, 6, 6-Cl, 7 and 8),
1H, 13C-2D HETCOR (for 4, 6, 6-Cl, 7 and 8), and 31P
NMR (for 4, 6, 6-Cl, 7, 8, 10, and 11) data have been
provided as PDF file.
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Acknowledgements
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Authors like to thank the Korea Research Founda-
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nancial support of this study.
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