π-Allyliridium(I) complexes, Ir(η3-CH2CHCHAr)(CO)(PPh3)2 (Ar=Ph, C6H4Me-p, C6H4Br-p). Comparison of their structures and chemical properties with analogous Rh complexes

Article abstract of DOI:10.1016/S0022-328X(00)00142-X

Arylallenes such as (4-methylphenyl)allene, phenylallene, and (4-bromophenyl)allene react with IrH(CO)(PPh₃)₃ to give the π-allyliridium(I) complexes, Ir(η³-CH₂CHCHAr)(CO)(PPh₃)₂ (Ar=C₆H₄Me-p, Ph, and C₆H₄Br-p). Crystallographic studies of the complexes showed a similar coordination geometry to that of Rh(η³-CH₂CHCHX)(CO)(PPh₃)₂. An equimolar reaction of phenylacetylene with Ir(η³-CH₂CHCHC₆H ₄Me-p)(CO)(PPh₃)₂ gives a mixture of trans-Ir(CCPh)(CO)(PPh₃)₂ and trans,trans-IrH(CCPh)₂(CO)(PPh₃)₂ accompanied by the liberation of 1-(4-methylphenyl)-1-propene. The Ir(III) acetylide complex is obtained separately from the reaction of excess phenylacetylene with the π-allyliridium(I) complex. The respective square-planar and octahedral structures of these complexes are determined by X-ray and NMR analyses. The NMR spectra of the reaction mixture indicate concurrent formation of the Ir(I) and Ir(III) complexes having the phenylethynyl ligands.

Full text of DOI:10.1016/S0022-328X(00)00142-X

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Journal of Organometallic Chemistry 602 (2000) 144–150
p-Allyliridium(I) complexes, Ir(h3-CH2CHCHAr)(CO)(PPh3)2
(Ar=Ph, C6H4Me-p, C6H4Br-p). Comparison of their structures
and chemical properties with analogous Rh complexes
Kohtaro Osakada *, Masayuki Kimura, Jun-Chul Choi
Research Laboratory of Resources Utilization, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan
Received 13 December 1999; received in revised form 7 February 2000; accepted 15 February 2000
Abstract
Arylallenes such as (4-methylphenyl)allene, phenylallene, and (4-bromophenyl)allene react with IrH(CO)(PPh3)3 to give the
p-allyliridium(I) complexes, Ir(h3-CH2CHCHAr)(CO)(PPh3)2 (Ar=C6H4Me-p, Ph, and C6H4Br-p). Crystallographic studies of
the complexes showed a similar coordination geometry to that of Rh(h3-CH2CHCHX)(CO)(PPh3)2. An equimolar reaction of
phenylacetylene with Ir(h3-CH2CHCHC6H4Me-p)(CO)(PPh3)2 gives a mixture of trans-Ir(CꢀCPh)(CO)(PPh3)2 and trans,trans-
IrH(CꢀCPh)2(CO)(PPh3)2 accompanied by the liberation of 1-(4-methylphenyl)-1-propene. The Ir(III) acetylide complex is
obtained separately from the reaction of excess phenylacetylene with the p-allyliridium(I) complex. The respective square-planar
and octahedral structures of these complexes are determined by X-ray and NMR analyses. The NMR spectra of the reaction
mixture indicate concurrent formation of the Ir(I) and Ir(III) complexes having the phenylethynyl ligands. © 2000 Elsevier Science
S.A. All rights reserved.
Keywords: Iridium; Allene; p-Allyl complex; Insertion; Alkynyl complex
of allene to hydridorhodium complexes to afford sev-
eral p-allyl rhodium complexes which served as in-
itiators of the polymerization of arylallenes and their
copolymerization with CO. As depicted in Scheme 1(i),
the reaction of excess phenylallene with RhH(PPh3)4
gives the complex containing a tetramer of arylallene
as the p-allyl ligand (A) [11d]. Complex A is the sole
product even in the equimolar reaction. The complex
Rh(h3-CH2CHCHPh)(PPh3)2 seems to be formed in
the reaction but is not observed in the reaction mixture
probably because it undergoes rapid further insertion
of phenylallene into the Rhꢁp-allyl bond. On the other
hand, an equimolar reaction of phenylallene with
RhH(CO)(PPh3)3 affords the product of insertion of
a single molecule of phenylallene into the RhꢁH
bond, Rh(h3-CH2CHCHPh)(CO)(PPh3)2 (B), in a high
yield (ii) [12]. Complex B with an 18 electron configu-
ration is stable enough to be isolated, but it reacts with
an excess amount of phenylallene to cause elimination
of the carbonyl ligand and insertion of three phenylal-
lene molecules into the Rhꢁp-allyl bond to give A
together with B (Scheme 1(iii)). Chemistry of the
1. Introduction
p-Allyl iridium complexes [1–6] were regarded as
stable and less reactive than the p-allyl complexes of
1st and 2nd row late transition metals such as Ni, Pd,
Fe, Ru, and Co which play important roles in various
CꢁC bond forming reactions, as well as polymerization
and oligomerization of alkenes and dienes via p-allyl
intermediates. Recent reports on unique reactivity of
the p-allyliridium complexes toward nucleophiles [7,8]
as well as an efficient allyl alkylation using an Ir
catalyst [9] have reinforced attention to the properties
of p-allyliridium complexes.
One of the convenient methods to prepare p-al-
lyliridium complexes is the reaction of diene with hy-
dridoiridium complexes leading to the insertion of a
double bond into the IrꢁH bond [10]. In the course of
study of Rh complex promoted oligomerization and
polymerization of arylallenes [11], we found insertion
* Corresponding author. Fax: +81-45-9245224.
E-mail address: kosakada@res.titech.ac.jp (K. Osakada)
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 0 ) 0 0 1 4 2 - X

K. Osakada et al. / Journal of Organometallic Chemistry 602 (2000) 144–150
145
above insertion of allene into the MꢁH and MꢁC bond
and of the resulting p-allyl complexes of other transition
metals is of a significant interest from the viewpoint of
its relevance to the mechanism of late transition metal
complex catalyzed polymerization and oligomerization
of allenes, dienes and other unsaturated molecules. In
this paper we report structure and reactions of p-al-
lyliridum complexes and the comparison of their proper-
ties with those of analogous Rh complexes.
ORTEP drawings of 1 and 3 whose crystals are iso-
morphous to each other and also to Rh(h3-
CH2CHCHC6H4Me-p)(CO)(PPh3)2 [12]. The angles of
coordination bonds (Table 1) resemble among these three
Rh and Ir complexes. Since the angles, made up of the
bonds, IrꢁP1, IrꢁP2, IrꢁC1, and IrꢁC3 fall in the range,
96–119°, the structure of the complexes is represented as
a somewhat distorted tetrahedral composed of the four
ligands around the Ir center or a piano-stool type
coordination having the p-allyl ligand at the top.
(1)
2. Results and discussion
The reaction of arylallenes such as (4-
methylphenyl)allene, phenylallene, and (4-bromopheny-
lallene) with IrH(CO)(PPh3)3 leads to the insertion of a
double bond of the substrate into the IrꢁH bond to give
p-allylirdium(I)
complexes
Ir(h3-CH2CHCHAr)-
The NMR (1H, 13C{1H}, and 31P{1H}) spectra of 1–3
in solutions provided information about the structures in
solution. The 13C{1H}-NMR spectrum of 1 contains
three signals l 67.8, 55.5, and 29.8 which are assigned to
CH(ꢁAr), CH, and CH2 carbons of the p-allyl ligand,
respectively, based on its comparison with the gated
decoupled spectrum (1J(CH)=150–173 Hz) and
(CO)(PPh3)2 (1: Ar=C6H4Me-p, 2: Ar=Ph, 3: Ar=
C6H4Br-p) as shown in Eq. (1). The insertion proceeds
smoothly at room temperature (r.t.) similarly to the
already reported reaction of the unsubstituted allene [10]
and shows no significant difference in the reaction rate
from the reaction with RhH(CO)(PPh3)3. Fig. 1 depicts
Scheme 1.
Fig. 1. ORTEP drawings of (a) 1 and (b) 3 at 30% ellipsoidal levels.

146
K. Osakada et al. / Journal of Organometallic Chemistry 602 (2000) 144–150
Table 1
peak is separated to two signals at l 1.15 and −0.18.
,
Selected bond distances (A) and angles (°) of 1 and 3
The signals Ha–Hd are assigned as shown in Scheme 2(i)
1
based on homodecoupled H-NMR spectra and on the
1
3
Rh complex a
comparison with data of the Rh complexes. The 31P{1H}-
NMR spectra of 1 exhibit a temperature depend-
ent change; two doublets (J(PP)=50 Hz) observed at
−70°C coalesce on raising the temperature and is turned
to a broad single peak at 20°C (Fig. 3). This fluxional
behavior of the complex is attributed to a p–s–p
rearrangement of the allyl ligand on the NMR time scale
shown in Scheme 2(ii). The rearrangement of the p-allyl
ligand renders the two PPh3 ligands equivalent in the
tetrahedral type coordination of the complex. Difference
in the coalescence temperature between the 31P{1H}- and
the 1H-NMR signals (ca. 5°C) is smaller than that
expected from the peak separation of the 31P{1H} and
Bond distances
IrꢁP1
IrꢁP2
IrꢁC1
C1ꢁO1
IrꢁC2
IrꢁC3
IrꢁC4
C2ꢁC3
C3ꢁC4
2.299(4)
2.365(5)
1.86(2)
1.15(2)
2.18(2)
2.14(2)
2.19(2)
1.37(3)
1.41(2)
2.295(6)
2.367(6)
1.82(2)
1.19(3)
2.24(2)
2.11(3)
2.24(2)
1.40(4)
1.43(4)
2.318(2)
2.443(2)
1.839(8)
1.163(8)
2.199(8)
2.145(8)
2.238(8)
1.42(1)
1.41(1)
Bond angles
P1ꢁIrꢁP2
P1ꢁIrꢁC1
P2ꢁIrꢁC1
P1ꢁIrꢁC2
P1ꢁIrꢁC3
P1ꢁIrꢁC4
P2ꢁIrꢁC2
P2ꢁIrꢁC3
P2ꢁIrꢁC4
C1ꢁIrꢁC3
IrꢁC1ꢁO
112.5(2)
95.7(5)
106.2(6)
91.6(5)
108.8(5)
146.1(5)
97.9(6)
118.1(5)
95.2(5)
112.8(4)
174(2)
112.5(2)
95.6(7)
107.4(7)
90.6(5)
108.4(8)
146.1(6)
98.6(6)
118.4(7)
95.0(7)
112(1)
112.61(8)
97.1(2)
106.0(3)
91.2(2)
109.8(2)
146.4(2)
97.0(2)
116.8(2)
94.9(2)
1
signals (ca. 1760 Hz) and the H-NMR signals (ca. 520
Hz). The small degree of disagreement of the kinetic
parameters obtained from the independent NMR mea-
surements can be attributed to the unsatisfactory control
of temperature of the solution during the 31P-NMR
measurement with 1H irradiation rather than to the
presence of another fluxional process of the molecule.
The equimolar reaction of phenylacetylene with p-al-
lyliridium complex 1 at 50°C gives a mixture of trans-
Ir(CꢀCPh)(CO)(PPh3)2 (4) and trans,trans-IrH(CO)(Cꢀ
CPh)2(PPh3)2 (5) accompanied by liberation of 1-(4-
methylphenyl)-1-propene as shown in Eq. (2). Complex
4 was separated from the reaction mixture and character-
ized by comparison of the positions of 31P{1H}- and the
13C{1H}-NMR (acetylide carbons) signals with those of
authentic sample [13]. Complex 5 was prepared separately
from the reaction of excess phenylacetylene with 1. Both
complexes were isolated as crystals suited for X-ray
analyses. Fig. 4 depicts ORTEP drawings of the molecules.
Molecule of 4 is composed of phenylethynyl, CO, and
PPh3 ligands forming a square-planar geometry around
the metal center with two phosphine ligands at trans
positions. Complex 5 has an octahedral coordination
although position of the hydrido was not determined in
the crystallographic results. Table 2 summarizes selected
bond distances and angles. A much longer bond between
112.8(4)
174.1(8)
116.7(8)
175(2)
117(2)
C2ꢁC3ꢁC4
114(2)
a Rh(h3-CH2CHCHC6H4Me-p)(CO)(PPh3)2. Taken from Ref. [5].
Distances and angles of bond including Rh are shown.
,
the carbonyl carbon and Ir (IrꢁC1, 2.23 A) of 5 than the
,
corresponding bond distances of 4 (1.78–1.82 A) is partly
duetoalarge trans influenceofthehydrido ligand situated
at the trans position of the alkynyl ligand of 5. The
presence of the hydrido ligand was confirmed unambigu-
Fig. 2. Temperature dependent 1H-NMR spectra of 1 (in CD2Cl2;
p-allyl ligand hydrogen region). Peaks with asterisks are due to
impurities (probably water) contaminated during the sample prepara-
tion.
1
ously by the H-NMR spectrum of 5 showing a triplet
signal at l −8.17 with J(PH) of 15 Hz.
on the peak positions. Fig. 2 summarizes temperature
dependent 1H- and 31P-NMR spectra of 1 (CD2Cl2). The
spectrum at 25°C contains two CH hydrogen signals of
the allyl ligand, Ha and Hb, at l 4.15 and 2.72, while a
broad peak due to CH2 hydrogens is observed at l
0.8–0.7. On cooling the solution to −70°C, the broad
(2)

K. Osakada et al. / Journal of Organometallic Chemistry 602 (2000) 144–150
147
Scheme 2.
unless otherwise stated. Elemental analyses were carried
out by Yanaco MT-5 CHN Autocorder.
The reaction of phenylacetylene with 1 was moni-
1
tored by H- and 31P{1H}-NMR spectra of the reaction
a
IrH(CO)(PPh3)3 [16] and arylallenes [17] were prepared
according to the literature.
mixture. Fig. 5 plots amounts of the two complexes
during the 5:1 molar reaction at 50°C. The signals of 4
and 5 are observed from the beginning of the reaction
and grow in parallel during the initial 10 h. After 21 h,
1 is consumed to leave a mixture of 4 and 5. Further
reaction of phenylacetylene with 4 leads to the conver-
sion of all the complexes to 5. Similar reaction of
phenylacetylene with Rh(h3-CH2CHCHAr)(CO)(PPh3)2
gives the monoalkynylrhodium(I) complex as the sole
product even when excess amounts of phenylacetylene
was allowed to react [11d]. Oxidative addition of CꢁH
bond of ethylene to Ir(I) complexes with tripodal amine
ligands giving Ir(III) complex occurs more easily than
the reaction with the corresponding Rh(I) complexes
[14,15].
3.1. Reaction of arylallenes with IrH(CO)(PPh3)3
To a toluene (10 cm3) solution of IrH(CO)(PPh3)3 (90
mg, 90 mmol) was added (4-methylphenyl)allene (12 mg,
92 mmol) at r.t. After stirring the reaction mixture for
20 h, the solvent was removed under vacuum. The
resulting oily material was washed repeatedly with hex-
ane to give 1 as a yellow solid (78 mg, 98%). Recrystal-
lization of the product from THF–hexane gave yellow
single crystals suited for X-ray analysis (60 mg, 75%).
Anal. Calc. for C47H41OP2Ir: C, 64.44; H, 4.68. Found
1
C, 64.41; H, 4.90%. H-NMR (400 MHz at 25°C in
C6D6): l 7.51 (d, 2H, C6H4, J=8 Hz), 7.50–7.46 (m,
14H, PPh3 (ortho) and C6H4), 6.98–6.96 (m 18H, PPh3
(meta and para)), 4.58 (1H, q, Ha, J=6 Hz), 3.17 (1H,
q, Hb, J=6 Hz), 2.16 (s, 3H, CH3), 1.1 (br, 2H, Hc and
Hd); (400 MHz at 25°C in CD2Cl2): l 7.33–7.06 (m,
34H, aromatic), 4.15 (q, 1H, Ha, J=6Hz), 2.72 (q, 1H,
Hb, J=6 Hz), 2.30 (s, 3H, CH3), 0.8–0.7 (br, 2H, Hc
and Hd); (400 MHz at −70°C in CD2Cl2): l 7.33–7.06
(m, 34H, aromatic), 3.98 (m, 1H, Ha), 2.60 (dt, 1H, Hb,
J=18 and 7 Hz), 2.28 (s, 3H, CH3), 1.15 (m, 1H, Hc),
−0.18 (dd, 1H, Hd, J=24 and 6 Hz). 13C-NMR (100
MHz at 25°C in C6D6): l 185.1 (CO), 142.1, 137.7,
137.3, 135.5, 134.7, 133.8, 133.1, 131.7, 129.9, 129.3,
129.1, 128.8, 127.5, 127.2, 126.7, 126.1, 67.8 (CHAr,
The reaction of arylallene with IrH(CO)(PPh3)3
shown in this study smoothly gives the p-allyliridium
complexes, Ir(h3-CH2CHCHAr)(CO)(PPh3)2, similarly
to RhH(CO)(PPh3)3. The Ir complexes do not react
with arylallenes on further addition of excess arylallene
at r.t., whereas the Rh complexes were reported to
undergo multiple insertion of arylallene molecules into
the p-allylꢁRh bond. The latter reaction seems to be
triggered by initial dissociation of the CO ligand to give
coordinatively unsaturated Rh(h3-CH2CHCHAr)-
(PPh3)2 which undergoes rapid insertion of arylallene
molecules into the RhꢁC bond until complex A in
Scheme 1 with a sterically demanding p-allyl ligand is
formed.
In summary, chemistry of the p-allyliridium com-
plexes shown here has several characteristics uncom-
mon to the version of p-allylrhodium complexes.
Further studies on chemical properties of the p-allyl
complexes of Group 9 transition metals would provide
new aspects of the stoichiometric and catalytic reac-
tions promoted by these metal complexes.
3. Experimental
Manipulations of the complexes were carried out
under nitrogen or argon using standard Schlenk tech-
nique. The NMR spectra (1H, 13C, and 31P) were
recorded on a JEOL EX-400 spectrometer at 25°C
Fig. 3. Temperature dependent 31P{1H}-NMR spectra of
CD2Cl2).
1 (in

148
K. Osakada et al. / Journal of Organometallic Chemistry 602 (2000) 144–150
Fig. 4. ORTEP drawings of (a) 4 and (b) 5. One of the two crystallographically independent molecules of 4 is shown. The molecule of 5 contains
a crystallographic C2 symmetry around the Ir center. The atoms with asterisks at the numbers are crystallographically equivalent to those with
the same number without asterisk. C1 and O atoms are expressed by a simple ball–stick model. One of the crystallographically equivalent
carbonyl ligands is omitted for simplicity. The hydrido of 5 was not located.
methylphenyl)-1-propene (100%). The product was
washed several times with hexane to give a mixture of
orange crystals (19 mg) and a dark orange solid (73
mg). The former crystals, separated from the solid, were
characterized by X-ray crystallography and comparison
of the NMR data with authentic sample and identified
to trans-Ir(CꢀCPh)(CO)(PPh3)2 (4). IR (KBr, cm−1):
1962 [w(CꢀO)]. 1H-NMR (400 MHz at 25°C in C6D6): l
7.93, 7.00 (m, 35H, C6H5). 13C{1H}-NMR (75 MHz in
CDCl3): l 125.1 (IrꢁC), 127.3 (CꢀCPh). 31P{1H}-NMR
(160 MHz at 25°C in C6D6): l 4.63 (s). The NMR
spectra of the remaining dark orange solid contained
the signals of trans,trans-IrH(CꢀCPh)2(CO)(PPh3)2 (5)
and unreacted 1.
J(CH)=173 Hz), 55.5 (CH, J(CH)=156 Hz), 29.8
(CH2, J(CH)=150 Hz), 21.3 (CH3, J(CH)=125 Hz).
31P{1H}-NMR (160 MHz at 25°C in C6D6): l 9.8 (br);
(160 MHz at −70°C in CD2Cl2) 15.0 and 4.1 (d,
J(PP)=50 Hz).
Complexes 2 and 3 were obtained analogously in 75
and 53%, respectively. Data of 2. Anal. Calc. for
C46H39OP2Ir: C, 64.12; H, 4.53. Found C, 64.04; H,
1
4.88%. IR (KBr, cm−1): 1939 [w(CꢀO)]. H-NMR (400
MHz at 25°C in C6D6): l 7.56 (d, 2H, C6H5 (ortho),
J=8 Hz), 7.50–7.40 (m, 12H, PPh3 (ortho)), 7.31 (t,
C6H5 (para), J=8 Hz), 7.05–6.90 (m, 20H, PPh3 (ortho
and para) and C6H5 (meta)), 4.57 (1H, q, Ha, J=6 Hz),
3.13 (1H, q, Hb, J=6 Hz), 1.1 (br, 2H, Hc and Hd).
13C{1H}-NMR (100 MHz at 25°C in C6D6): l 185.0
(CO), 145.1, 137.6, 137.2, 133.9, 133.8, 129.2, 128.5,
128.3, 127.9, 126.8, 125.1, 67.6 (CHAr), 55.25 (CH),
29.6 (CH2). 31P{1H}-NMR (160 MHz at 25°C in C6D6):
l 9.5 (br). Data of 3. Anal. Calc. for C46H38BrOP2Ir: C,
58.74; H, 4.04. Found C, 58.85; H, 4.14%. IR (KBr,
Complex 5 was prepared separately from the reaction
of an excess amounts of phenylacetylene with 1. To a
Table 2
,
Selected bond distances (A) and angles (°) of 4 and 5
a
4
5
1
cm−1): 1935 [w(CꢀO)]. H-NMR (400 MHz at 25°C in
Bond distances
C6D6): l 7.40–7.37 (m, 14H, PPh3 (ortho) and C6H4),
7.21 (d, 2H, C6H4Br), 6.9 (br, 18H, PPh3 (meta and
para)), 4.42 (1H, q, Ha, J=6 Hz), 2.93 (1H, q, Hb,
J=6 Hz), 1.07 (br, 2H, Hc and Hd); 13C{1H}-NMR
(100 MHz at 25°C in C6D6): l 184.4 (CO), 144.1, 136.8,
136.3, 133.4, 133.3, 130.9, 129.0, 127.8, 127.6, 117.4,
66.7 (CHAr), 52.3 (CH), 29.0 (CH2). 31P{1H}-NMR
(160 MHz at 25°C in C6D6): l 8.8 (br).
IrꢁP1
IrꢁP2
IrꢁC1
C1ꢁO1
IrꢁC2
C2ꢁC3
2.286(7) [2.313(9)]
2.291(6) [2.309(9)]
1.82(3) [1.78(3)]
1.18(3) [1.20(3)]
2.04(2) [1.99(3)]
1.21(3) [1.22(3)]
2.329(5)
–
2.23(5)
1.18(5)
2.04(2)
1.15(2)
Bond angles
P1ꢁIrꢁP2
P1ꢁIrꢁC1
P1ꢁIrꢁC2
P2ꢁIrꢁC1
P2ꢁIrꢁC2
C1ꢁIrꢁC2
IrꢁC1ꢁO
173.3(2) [174.7(2)]
91(1) [91(1)]
87(1) [92(1)]
95(1) [93(1)]
87(1) [85(1)]
174.4(2) [177(1)]
177(2) [179(3)]
174(2) [173(2)]
179(3) [174(3)]
–
180.0
89(1)
92.5(5)
–
3.2. Reaction of phenylacetylene with 1
–
92(1)
165(4)
174(2)
178(2)
180.0
To a benzene (10 cm3) solution of 1 (97 mg, 0.11
mmol) was added phenylacetylene (11 mg, 0.11 mmol)
at 50°C. Color of the solution changed from yellow to
orange during the heating. After 60 h, the solvent was
evaporated to dryness under vacuum. The 1H-NMR
analyses of the product showed formation of 1-(4-
IrꢁC2ꢁC3
C2ꢁC3ꢁC4
C1ꢁIrꢁC1
a Bond parameters of one of the crystallographically independent
molecules are shown in brackets.

K. Osakada et al. / Journal of Organometallic Chemistry 602 (2000) 144–150
149
Table 3
Crystallographic data and details of structure refinement
Complex
1
3
4
5
Formula
C
875.74
0.3×0.3×0.4
Monoclinic
P21/c (no. 14)
9.589(2)
47H41OP2Ir
C46H38BrOP2Ir
940.63
0.1×0.1×0.9
Monoclinic
P21/c (no. 14)
9.613(3)
C45H35OP2Ir
845.94
0.1×0.2×0.4
Triclinic
C53H41OP2Ir
947.80
0.2×0.2×0.4
Monoclinic
P21/n (no. 14)
13.364(2)
Formula weight
Dimensions (mm)
Crystal system
Space group
(
P1 (no. 2)
,
a (A)
12.329(6)
35.01(1)
9.424(5)
93.85(4)
106.16(5)
96.60(6)
3861(1)
4
,
b (A)
18.400(4)
21.746(2)
18.355(4)
21.740(3)
9.280(1)
17.419(1)
,
c (A)
h (°)
i (°)
k (°)
91.981(1)
91.92(2)
97.171(9)
3
,
V (A )
3834(1)
4
1.517
1752
3.61
9617
3834(1)
4
1.630
1856
4.656
2143.3(4)
2
1.469
948
3.236
5432
5217
Z
zcalc. (g cm−3
F(000)
)
1.455
1680
3.583
10061
v(Mo–Ka) (mm−1
)
Reflection measured
Unique reflections
9614
9090
9091
10059
(Rint=0.109)
3589
(Rint=0.101)
(Rint=0.118)
6287
(Rint=0.074)
2028
Used reflections
(I\1.5|(I))
Variables
3529 a
460
460
883
258
R (Rw)
0.059 (0.062)
0.050 (0.060)
0.065 (0.079)
0.080 (0.092)
a (I\1.0|(I)).
1
toluene (10 cm3) solution of 1 (172 mg, 0.17 mmol) was
added phenylacetylene (174 mg, 1.7 mmol) at 50°C.
After heating for 47 h, the solvent was evaporated to
dryness under vacuum. The product was washed with
hexane to give 5 as a solid (70 mg, 43%). Recrystalliza-
tion from toluene–hexane gave yellow single crystals
suited for X-ray analyses (32 mg, 20%). Anal. Calc. for
C53H41OP2Ir: C, 67.17; H, 4.33. Found C, 66.83 H,
4.32%. IR (KBr, cm−1): 2010 [w(CꢀO)], 2122 [w(IrꢁH)],
2350 [w(CꢀC)]. H-NMR (400 MHz at 25°C in C6D6): l
8.00–7.00 (m, 40H, C6H5), −8.17 (t, 1H, IrꢁH, J
(HP)=15 Hz). 13C{1H}-NMR (100 MHz at 25°C in
C6D6): l 134.6, 132.6, 132.0, 130.8, 130.2, 129.0, 127.8,
127.1, 124.2, 109.2 (CꢁPh), 82.0 (t, IrꢁC, J(PC)=13
Hz). 31P{1H}-NMR (160 MHz at 25°C in C6D6): l 1.1.
3.3. X-ray crystallography
Crystals of 1, 3 4, and 5 suitable for X-ray diffraction
study were obtained by recrystallization from THF–
hexane (1) and toluene–hexane (3–5), and mounted in
glass capillaries under argon. Data were collected at
23°C on a Rigaku AFC-5R automated four-circle dif-
fractometer equipped with monochromated Mo–Ka ra-
,
diation (u=0.71073 A). Calculations were carried out
by using a program package TEXSAN for Windows. The
structures were solved by a direct method and subse-
quent Fourier technique. All non-hydrogen atoms were
refined anisotropically. The hydrogen atoms were lo-
cated by assuming the ideal geometry and included in
the structure calculation without further refinement of
the parameters. Crystallographic data and details of
refinement are summarized in Table 3.
4. Supplementary material
Fig. 5. Profile of the reaction of phenylacetylene with 1 in a 5:1 molar
ratio at 50°C in C6D6. Relative amounts of (a) 1, (b) 4, and (c) 5
determined by the 31P{1H}-NMR peak area ratio of the reaction
mixture are shown. The reaction after 25 h was carried out at 100°C.
Crystallographic data (excluding structural factors)
for the structure in the paper have been deposited with

150
K. Osakada et al. / Journal of Organometallic Chemistry 602 (2000) 144–150
Carmona, J. Am. Chem. Soc. 114 (1992) 7288.
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the Cambridge Crystallographic Data Centre as supple-
mentary publication no. CCDC 137738–137741.
Copies of this information may be obtained free of
charge from The Director, CCDC, 12 Union Road,
Cambridge, CB2 1EZ, UK (Fax: +44-1223-336-033;
e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
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Acknowledgements
[10] C.K. Brown, W. Mowat, G. Yagupsky, G. Wilkinson, J. Chem.
Soc. (A) (1971) 850.
This work was financially supported by a Grant-in-
aid for Scientific Research from the Ministry of Educa-
tion, Science, Sport and Culture, Japan. Authors are
grateful to Professor Takakazu Yamamoto of our Insti-
tute for helpful discussion throughout this study.
[11] (a) K. Osakada, J.-C. Choi, T. Yamamoto, J. Am. Chem. Soc.
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[12] K. Osakada, J.-C. Choi, T. Koizumi, I. Yamaguchi, T. Ya-
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