Metal-assisted preparation of the alkenyl ketone and carbonyl complexes from 1-alkyne and H2O: C-C triple bond cleavage of terminal alkyne

Article abstract of DOI:10.1016/j.ica.2005.12.003

Reactions of Cp*RhCl₂(PPh₃) (1) with 1-alkyne and H₂O in the presence of KPF₆ generated alkenyl ketone complexes [Cp*Rh(CRCHCOCH₂R)(PPh₃)](PF₆) (2) (R = Ph (a), C₆H₄-p-Me (b), C₆H ₄-p-COOMe (c), C₆H₄-p-NO₂ (d)). A similar complex [Cp*Rh(CPhCHCOCH₂Ph)(PMePh₂)] (PF₆) (2e) was obtained by use of Cp*RhCl ₂(PMePh₂). It was revealed by X-ray analyses of 2b, 2c and 2e that the complexes 2 consist of the five-membered ring structures bound by the carbon and oxygen atoms of the alkenyl ketone group. Similar reactions of Cp*IrCl₂(PPh₃) (6) or (C₆Me ₆)RuCl₂(PPh₃) (7) proceeded with a cleavage of C-C triple bond of 1-alkyne without formation of an alkenyl ketone complex, affording the corresponding carbonyl complexes, [Cp*IrCl(PPh ₃)(CO)](PF₆) (8) or [(C₆Me₆) RuCl(PPh₃)(CO)](PF₆) (9). The diphosphine complexes [(Cp*MCl₂)₂{μ-diphos}] (4: M = Rh, diphos = dppm,; 12a: M = Ir, diphos = dppm; 12b: M = Ir, diphos = dppb) gave a Cl-bridged rhodium complex [{Cp*Rh(μ-Cl)}₂{μ-dppm}](PF ₆)₂ (5), mono-carbonyl or dicarbonyl iridium complexes,[(Cp*IrCl₂){μ-dppm}{Cp*IrCl(CO)}](PF ₆)(13a) or [{Cp*IrCl(CO)}₂{μ-dppb}](PF ₆)₂ (14b), respectively.

Full text of DOI:10.1016/j.ica.2005.12.003

Inorganica Chimica Acta 359 (2006) 1549–1558
www.elsevier.com/locate/ica
Metal-assisted preparation of the alkenyl ketone and
carbonyl complexes from 1-alkyne and H2O: C–C triple bond
cleavage of terminal alkyne
a,
a
a
a
Kenichi Ogata *, Jyoji Seta , Kenichiro Sugawara , Naoko Tsutsumi ,
a
b
b,1
Yasuhiro Yamamoto , Katsuaki Kuge , Kazuyuki Tatsumi
a
Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan
Research Center for Materials Science and Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku,
Nagoya 454-8602, Japan
b
Received 30 September 2005; received in revised form 25 November 2005; accepted 4 December 2005
Available online 18 January 2006
Abstract
Reactions of Cp*RhCl2(PPh3) (1) with 1-alkyne and H2O in the presence of KPF6 generated alkenyl ketone complexes
[Cp*Rh(CR@CHCOCH2R)(PPh3)](PF6) (2) (R = Ph (a), C6H4ꢀp-Me (b), C6H4-p-COOMe (c), C6H4-p-NO2 (d)). A similar complex
[Cp*Rh(CPh@CHCOCH2Ph)(PMePh2)](PF6) (2e) was obtained by use of Cp*RhCl2(PMePh2). It was revealed by X-ray analyses of
2b, 2c and 2e that the complexes 2 consist of the five-membered ring structures bound by the carbon and oxygen atoms of the alkenyl
ketone group. Similar reactions of Cp*IrCl2(PPh3) (6) or (C6Me6)RuCl2(PPh3) (7) proceeded with a cleavage of C–C triple bond of 1-
alkyne without formation of an alkenyl ketone complex, affording the corresponding carbonyl complexes, [Cp*IrCl(PPh3)(CO)](PF6)
(8) or [(C6Me6)RuCl(PPh3)(CO)](PF6) (9). The diphosphine complexes [(Cp*MCl2)2{l-diphos}] (4: M = Rh, diphos = dppm,; 12a:
M = Ir, diphos = dppm; 12b: M = Ir, diphos = dppb) gave a Cl-bridged rhodium complex [{Cp*Rh(l-Cl)}2{l-dppm}](PF6)2 (5),
mono-carbonyl or dicarbonyl iridium complexes,[(Cp*IrCl2){l-dppm}{Cp*IrCl(CO)}](PF6)(13a) or [{Cp*IrCl(CO)}2{l-dppb}](PF6)2
(14b), respectively.
Ó 2005 Elsevier B.V. All rights reserved.
Keywords: Rhodium complex; Iridium complex; Ruthenium complex; Alkenyl ketone complex; Alkyne; C–C triple bond-cleavage
1. Introduction
fungal and antibacterial activities. Carmona and his co-
workers have reported that dimeric butenolides were gener-
ated by sequential insertion of phenylacetylene and carbon
monoxide into nickel-acyl bonds, in which alkenyl ketone
complexes are precursors of the butenolides [3]. The alke-
nyl ketone complexes have been usually generated by two
or more steps: (1) an initial formation of acyl complexes
and subsequent insertion of alkynes into metal-acyl bonds,
and (2) an initial preparation of the metal carbonyl
complexes and the photo-induced or thermal reactions of
them with acetylenes. The acyl complexes trans-
NiCl(COR)(PMe3)2 (R = Me, CH2SiMe3, CH2CMe3,
CH2C6H4-o-Me) reacted with phenylacetylene to give
trans-NiCl(PMe3)2{CPh@CH(COR)} [3]. The insertion of
unsymmetrical alkynes into the M–C bonds of molybde-
In metal-assisted organic syntheses the five-membered
unsaturated c-lactones are biologically important synthetic
targets [1,2]. For example, the a,b-butenolide ring is pres-
ent in a large number of biologically important natural
products and certain butenolides indicate antitumor, anti-
*
Corresponding author. Present address: Department of Materials
Chemistry, Graduate School of Engineering, Yokohama National Uni-
versity, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan. Tel./
fax: +81 45 339 3932.
E-mail addresses: d03sa101@ynu.ac.jp (K. Ogata), i45100a@nucc.cc.
nagoya-u.ac.jp (K. Tatsumi).
1
Fax: +81 52 789 2943.
0020-1693/$ - see front matter Ó 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2005.12.003

1550
K. Ogata et al. / Inorganica Chimica Acta 359 (2006) 1549–1558
num and tungsten acyls has been reported to afford alkenyl
ketone complexes [4]. The photo-induced reaction of
CpM(CO)3R (M = Mo, W) with R1C„CR2 generated
alkenyl ketone complexes [4]. The formation of a dinuclear
alkenyl ketone iron complex has also been reported which
results from the reaction of acyl complex with g2-alkyne
intermediate complex [5].
During our extended research on formation of carbonyl
complexes, we found that simple complexes
Cp*MCl2(PPh3) (M = Rh, Ir) led to a cleavage of the C–
C triple bonds of 1-alkyne or a double insertion of alkynes
in the presence of H2O and KPF6, affording carbonyl com-
plexes or alkenyl ketone complexes, depending on
metals. This paper reports the one-step synthesis of alkenyl
ketone complexes and a facile C–C triple bond-cleavage
of 1-alkyne. Part of this work has already been published
[9].
Recently, we have provided the activation of small mol-
ecules by complexes, [Cp*MCl(MDMPP-P,O)] (M = Rh,
Ir); Cp* = C5Me5; MDMPP-P,O = PPh2(2-O-6-MeOC6-
H3), where one ortho-methoxy group in (2,6-dimethoxy-
phenyl)diphenylphosphine (MDMPP) was demethylated
in the reactions with [Cp*MCl2]2 (M = Rh, Ir) (Scheme 1).
For example, when they were treated with secondary or
tertiary amines in the presence of KPF6, the cleavage of the
C–N bond of amines occurred readily, generating com-
plexes, [Cp*M(MDMPP-P,O)(RNH2)](PF6) (R = Et, Pr,
iPr, etc.), bearing a corresponding primary amine [6]. They
were also treated with 1-alkynes such as HC„CCOOMe,
PhC„CH and nBuC„CH, and disubstituted alkynes such
as ROOCC„CCOOR (R = Me, Et) in the presence of
KPF6, leading to unusual reactions; in the reaction with
HC„CCOOMe, an extraction of CO from an ester group
and the insertion of another 1-alkyne into an Rh–O bond
occurred, affording a seven-membered metallacycle, and
reactions with HC„CR (R = Ph, nBu) led to the formation
of complexes bearing five- and six-membered rings accom-
panying a double insertion of 1-alkynes into a Rh–O bond
[7,8]. In a previous paper we have briefly described that the
reaction of Cp*IrCl(MDMPP-P,O) with phenylacetylene
and H2O in the presence of KPF6 led to a cleavage of the
2. Experimental
2.1. General procedures
All manipulations were carried out under a nitrogen
atmosphere. Dichloromethane was distilled over CaH2
and diethyl ether was distilled over LiAlH4. Cp*RhCl2-
(PPh3) (1) [10], Cp*RhCl2(PMePh2) (1e) [10], Cp*IrCl2(PPh3)
(6) [10], (C6Me6)RuCl2(PPh3) (7) [11], [(Cp*MCl2)2(l-
dppm)] (M = Rh (4), Ir (12a); dppm = Ph2PCH2PPh2) [12]
and [(Cp*IrCl2)2(l-dppb)] (12b) (dppb = Ph2P(CH2)4PPh2)
[12] were prepared according to the literature methods.
Other reagents employed in this research were commercially
available and used without further purification. The infra-
red and electronic absorption spectra were measured
on FT/IR-5300 and U-best 30 instruments, respectively.
The NMR spectra were recorded on a Bruker AC250 spec-
1
trometer. H NMR spectra were measured at 250 MHz,
and 31P{1H} NMR spectra were measured at 101 MHz
using 85% H3PO4 as an external reference. All coupling
constants were recorded in Hz. Fast atom bombardment
(FAB) mass spectra were measured on a JMS-DX300
spectrometer. Elementary analyses were performed by Ana-
lytical Center, School of Pharmaceutical Science, Toho
University.
C–C triple bond, affording
a
carbonyl complex
[Cp*Ir(MDMPP-P,O)(CO)](PF6) [9].
+
R2NH or R3N
NH2R
M
2.2. Preparation of rhodium complexes
RPhP
MeO
O
2.2.1. Preparation of [Cp*Rh(PPh3){CPh@CHC(O)CH2-
Ph}](PF6) (2a)
+
R1
C
To a solution of [Cp*RhCl2(PPh3)] (1) (97.6 mg,
0.171 mmol), H2O (1.0 mL, 55 mmol) and KPF6 (58.4
mg, 0.317 mmol) in CH2Cl2 (10 mL) and acetone
(15 mL), phenylacetylene (0.2 mL, 1.8 mmol) was added
at room temperature. After stirring for 24 h, the solvent
was removed. The residue was washed with diethyl ether
and recrystallized from CH2Cl2 and diethyl ether, giving
a reddish brown complex (80.0 mg, 54.6%). FAB mass:
m/z = 721 ([M ꢀ 1]+), 459 ([M ꢀ PPh3 ꢀ 1]+). IR(nujol):
R2
R3
C
Rh
RC CH
KPF6
RPhP
C
O
Cl
O
MeO
C
M
R4
RPhP
MeO
+
ROOCC CH
RC CH / H2O
CO
C
Rh
O
COOR
RPhP
MeO
M = Rh, Ir
C
R1, R3 = H; R2, R4 = nBu
R1, R3 = Ph; R2, R4 = H
H
1588, 1543 (C@C, C@O), 839 (PF6) cmꢀ1 1H NMR
.
+
(CDCl3): d.19 (d, JHP = 2.7 Hz, Cp*, 15H), 3.16 and 3.42
(AB system, JHH = 16.0 Hz, CH2, 2H) 6.73(s, @CH, 1H),
6.9–7.8 (m, Ph, 25H). 31P{1H} NMR (CDCl3): d 38.0 (d,
JPRh = 152 Hz), ꢀ143.7 (sep, JPF = 712 Hz, PF6). Anal.
Calc. for C44H43P2F6ORh: C, 60.98; H, 5.00. Found: C,
61.03; H, 5.09%.
Ir
CO
O
RPhP
MeO
Scheme 1. Activation of small molecules by [Cp*MCl(MDMPP-P,O)].
The PF6 anions are omitted for clarity.

K. Ogata et al. / Inorganica Chimica Acta 359 (2006) 1549–1558
1551
2.2.2. Preparation of [Cp*Rh(PPh3){C(C6H4-p-Me)@
CHC(O)CH2(C6H4-p-Me)}](PF6) (2b)
NMR(CDCl3): d 17.9 (d, JRhP = 148 Hz), ꢀ143.6 (sep.
JRhP = 713 Hz, PF6). Anal. Calc. for C39H41OF6P2Rh: C,
58.22; H, 5.14. Found: C, 58.47; H, 5.44%.
Reddish brown crystals of 2b (41.4 mg, 42.9%) obtained
from 1 (70.9 mg, 0.124 mmol), H2O (1.0 mL, 55 mmol), p-
tolylacetylene (0.1 mL, 0.8 mmol) and KPF6 (46.7 mg,
0.254 mmol) according to a procedure similar to that of
2a. FAB mass: m/z: 749 [M ꢀ 1+]. IR(nujol): 1599, 1537
2.2.6. Preparation of [Cp*RhCl(PPh3){CNC6H4-
C„CH}](PF6) (3)
A mixture of 1 (82.7 mg, 0.145 mmol), KPF6 (88.9 mg,
0.483 mmol), H2O (1.0 mL, 55 mmol) and HC„CC6H4-4-
(NC) (52.4 mg, 0.412 mmol) in CH2Cl2 (10 mL) and acetone
(15 mL) was stirred at room temperature. The reddish brown
solution changed to yellow. After 24 h, the solvent was
removed and the residue was extracted with CH2Cl2. The
solution was concentrated to 2 mL and diethyl ether was
added, affording yellow complex of 3 (96.4 mg, 82.4%).
1
(C@O and C@C), 835 cmꢀ1 (PF6). H NMR (CDCl3): d
1.20 (d, JPH = 2.6 Hz, Cp*, 15H), 1.57 (s, p-Me, 3H),
2.34 (s, p-Me, 3H), 3.11, 3.29 (AB system, JHH = 16.0 Hz,
CH2, 2H), 6.67 (s, CH, 1H), ca. 6.9–7.8 (c, ArH). 31P{1H}
NMR(CDCl3): d 38.0 (d, JRhP = 151 Hz),ꢀ143.7 (sep.
JRhP = 712 Hz, PF6). Anal. Calc. for C46H47OF6P2Rh: C,
61.75; H, 5.29. Found: C, 61.73; H, 5.22%.
IR(nujol): 3279 (C„CH), 2174 (N„C), 843 (PF6) cmꢀ1
.
2.2.3. Preparation of [Cp*Rh(PPh3){C(C6H4-p-COOMe)@
CHC(O)CH2(C6H4-p-COOMe)}](PF6) (2c)
1H NMR (CDCl3): d 1.62 (d, JPH = 3.5 Hz, Cp*), 3.20 (s,
CH, 1H), 6.8-8.0 (c, ArH, 19H). 31P{1H} NMR(CD2Cl2): d
32.3 (d, JRhP = 122 Hz), ꢀ143.7 (sep. JRhP = 713 Hz, PF6).
Anal. Calc. for C37H35NClF6P2Rh: C, 55.00; H, 4.37; N,
1.73. Found: C, 55.19; H, 4.12; N, 1.95%.
Yellow crystals of 2c (61.4 mg, 50.7%) were obtained
from 1 (70.4 mg, 0.123 mmol), H2O (1.0 mL, 55 mmol),
HC„CC6H4-p-COOMe (49.7 mg, 0.310 mmol) and KPF6
(57.8 mg, 0.314 mmol) according to a procedure similar
to that of 2a. IR(nujol): 1717 (C@O), 1543 (C@O and
C@C), 833 cmꢀ1 (PF6). 1H NMR (CD2Cl2): d 1.21 (d,
JPH = 2.6 Hz, Cp*), 3.25, 3.58 (AB system, JHH = 16.5 Hz,
CH2, 2H),, 3.91 (s, Me, 3H), 3.93 (s, Me, 3H), 6.80 (s, CH,
1H), ca. 7.0–8.4 (c, ArH, 23H). 31P{1H} NMR(CD2Cl2): d
37.2 (d, JRhP = 148 Hz), ꢀ144.7 (sep. JRhP = 712 Hz, PF6).
Anal. Calc. for C48H47O5F6P2Rh: C, 58.66; H, 4.82.
Found: C, 58.94; H, 4.80%.
2.2.7. Preparation of [Cp*Rh(PPh3){CPh@CHC(O)-
CHDPh}](PF6)
To a solution of 1 (88.7 mg, 0.155 mmol), D2O (1.0 mL,
56 mmol) and KPF6 (71.6 mg, 0.389 mmol) in CH2Cl2
(10 mL) and acetone (10 mL), phenylacetylene (0.1 mL,
1.8 mmol) was added at room temperature. After stirring
for 6 h, the solvent was removed to dryness. The residue
was washed with diethyl ether and was extracted with
CH2Cl2. Removal of the solvent and the residue was recrys-
tallized from CH2Cl2 and diethyl ether, giving reddish
brown complex (69.7 mg, 51.7%). IR(nujol): 1543 (C@C,
2.2.4. Preparation of [Cp*Rh(PPh3){CC6H4-p-NO2@
CHC(O)CH2(C6H4-p-NO2)}](PF6) (2d)
Dark-brown crystals of 2d (33.2 mg, 24.2%) were
obtained from 1 (81.9 mg, 0.143 mmol), H2O (1.0 mL,
55 mmol), HC„CC6H4-p-NO2 (62.5 mg, 0.425 mmol)
and KPF6 (71.0 mg, 0.386 mmol) according to a procedure
similar to that of 2a. IR(nujol): 1510 (C@O and C@C),
843 cmꢀ1 (PF6). FAB mass: m/z 811 ([M ꢀ 1]+). 1H
NMR (CD2Cl2): d 1.23 (d, JPH = 2.6 Hz, Cp*), 3.28, 3.82
(AB system, JHH = 16.5 Hz, CH2, 2H), 6.90 (d,
JRhH = 2.0 Hz, CH, 1H), ca. 7.0–8.4 (c, ArH, 23H).
C@O), 839 (PF6) cmꢀ1 1H NMR (CDCl3): d 1.22 (d,
.
JHP = 2.5 Hz, Cp*, 15H), 3.16 (br-s, CHD, 1H), 6.78 (s,
H, 1H), 6.9–7.8 (m, Ph, 20H). 31P{1H} NMR(CDCl3): d
38.0 (d, JRhP = 153 Hz), ꢀ143.7 (sep. JPF = 713 Hz, PF6).
2.2.8. Preparation of [{Cp*Rh(l-Cl)}2 (dppm)](PF6)2
(5)
Orange crystals of 5 (20.8 mg. 44.8%) were obtained
from [(Cp*RhCl2)2(l-dppm)] (4) (38.1 mg, 0.038 mmol),
KPF6 (32.0 mg, 0.174 mmol), phenylacetylene (0.1 mL,
0.913 mol) and H2O (0.1 mL, 5.6 mmol) according to a
procedure similar to that of 2a. FAB mass: m/z 1074
31P{1H} NMR(CD2Cl2):
d 37.1 (d, JRhP = 148 Hz),
ꢀ144.6 (sep. JRhP = 712 Hz, PF6). Anal. Calc. for
C44H41N2O5F6P2Rh: C, 55.24; H, 4.32; N, 2.93. Found:
C, 55.02; H, 4.33; N, 3.12%.
1
([M + PF6]+), 931 ([M]+). IR (nujol): 835 (PF6) cmꢀ1. H
NMR (CD3COCD3): d 1.49 (d, JHP = 3.5 Hz, Cp*, 30H),
4.30 (t, JHP = 12.0 Hz, CH2, 2H), 7.4–7.7 (m, Ph, 15H).
31P{1H} NMR(CD3COCD3): d 25.4 (d, JPRh = 147.0 Hz),
ꢀ143.3 (sep. JPF = 712 Hz, PF6). Anal. Calc. for
C45H52P4Cl2F12Rh2: C, 44.25; H, 4.29. Found: C, 44.53;
H, 4.22%.
2.2.5. Preparation of [Cp*Rh(PMePh2)-
{CPh@CHC(O)CH2 Ph}](PF6) (2e)
Yellow crystals of 2e (54.1 mg, 61.5%) were obtained
from Cp*RhCl2(PMePh2) (1e) (55.7 mg, 0.11 mmol), phe-
nylacetylene (0.1 mL, 0.9 mmol), H2O (1.0 mL, 55 mmol)
and KPF6 (43.6 mg, 0.237 mmol) according to a procedure
similar to that of 2a. IR(nujol): 1545 (C@O or C@C), 839
2.3. Preparation of iridium and ruthenium complexes
1
(PF6) cmꢀ1. H NMR (CDCl3): d 1.25 (d, JPH = 2.5 Hz,
Cp*, 15H), 2.07 (d, JPH = 9.0 Hz, Me, 3H), 3.61, 3.72
(AB system, JHH = 15.5 Hz, CH2, 2H), 6.65 (d,
JRhH = 2.0 Hz, CH, 1H), 6.8–8.0 (c, ArH, 19H). 31P{1H}
2.3.1. Preparation of [Cp*IrCl(PPh3)(CO)](PF6) (8)
To a solution of 6 (101 mg, 0.152 mmol) and NaPF6
(96.5 mg, 0.575 mmol) in CH2Cl2 (15 mL) and acetone

1552
K. Ogata et al. / Inorganica Chimica Acta 359 (2006) 1549–1558
(15 mL), phenylacetylene (0.5 mL, 4.6 mmol) and H2O
(0.5 mL, 28 mmol) were added at room temperature. After
20 h, the solvent was removed to dryness and the residue
was extracted with CH2Cl2. The solvent was removed
and the residue was recrystallized from CH2Cl2 and diethyl
ether, affording yellow crystals of 8 (88.0 mg, 72.3%). FAB
mass: m/z 653 ([M]+), 625 ([M ꢀ CO]+), 363
([M ꢀ CO ꢀ PPh3]+). IR(nujol): 2049 (C„O), 841 (PF6)
15H), 7.3–7.8 (m, Ph, 15H). 31P{1H} NMR(CDCl3): d
1.51 (s, PPh3), ꢀ144.1 (sep. JPF = 712 Hz, PF6). Anal. Calc.
for C29H30OClF6P2Ir: C, 43.64; H, 3.79. Found: C, 43.77;
H, 3.81%.
for C50H58O2Cl2F12P4Ir2: C, 38.05; H, 3.78. Found: C,
38.06; H, 3.85%.
2.4. Reaction of 2a with HBF4
A mixture of 2a (43.4 mg, 0.05 mmol) and HBF4
(0.1 mL, 48 wt.% aq., 0.76 mmol) in CH2Cl2 (10 mL) was
stirred at room temperature. After 12 h, the solvent was
removed and the residue was extracted with CH2Cl2. The
solution was concentrated and diethyl ether was added,
recovering orange crystals of 2a (13.9 mg, 32.0%). The
work-up of the mother liquor gave a yellow solid of the
BF4 compound (15.6 mg, 38.7%). The structure was deter-
mined in comparison with the spectroscopic data of 2a.
1
cmꢀ1. H NMR (CDCl3): d 1.74 (d, JHP = 2.5 Hz, Cp*,
2.3.2. Preparation of [(C6Me6)RuCl(PPh3)(CO)](PF6)
(9)
2.5. X-ray crystallography – data collection
Yellow crystals of 9 (69.6 mg, 46.7%) were obtained
from (C6Me6)RuCl2(PPh3) (7) (121 mg, 0.20 mmol),
NaPF6 (146 mg, 0.87 mmol), phenylacetylene (0.3 mL,
2.7 mmol) and H2O (1.5 mL, 83 mmol) according to a pro-
cedure similar to that of 8. FAB mass: m/z 590 ([M ꢀ 1]+),
562 ([M ꢀ CO ꢀ 1]+). IR(nujol): 1985 (C„O), 837 (PF6)
7.4–7.7 (m, Ph, 15H). 31P{1H} NMR(CD3COCD3): d
42.1 (s, PPh3), ꢀ143.3 (sep. JPF = 712 Hz, PF6). Anal. Calc.
for C31H33OClF6P2Ru: C, 50.72; H, 4.53. Found: C, 50.29;
H, 4.53%.
All complexes were recrystallized from CH2Cl2/diethyl
ether. Cell constants of 2b and 2e Æ Et2O were determined
from 20 reflections on a Rigaku AFC5S diffractometer.
Data collections were carried out on a Rigaku AFC5S dif-
fractometer. Intensities were measured by the 2h ꢀ x scan
1
cmꢀ1. H NMR (CD3COCD3): d 2.05 (s, C6Me6, 18H),
method using Mo Ka radiation (k = 0.71069 A) at 24°.
˚
Throughout the data collection the intensities of the three
standard reflections were measured every 200 reflections
as a check of the stability of the crystals and no decay
was observed. Absorption corrections were made with w
scans. Crystal of 2c was mounted at the top of quartz fiber
using perfluoro(polyoxopropylene ethylether), which was
set on a MSC/ADSC Quantum CCD/Rigaku AFC8 (ult-
raX 18) diffractometer. The measurement was made by
2.3.3. Preparation of [{Cp*IrCl(CO)}{Cp*IrCl2}-
(dppm)](PF6) (13a)
Yellow crystals of 13a (26.8 mg, 47.3%) were obtained
from [(Cp*IrCl2)2(l-dppm)] (12a) (51.2 mg, 0.043 mmol),
KPF6 (43.0 mg, 0.219 mmol), phenylacetylene (0.1 mL,
0.913 mmol) and H2O (0.1 mL, 5.6 mmol) according to a
procedure similar to that of 8. FAB mass: m/z 1172
([M ꢀ 1]+), 775 ([M ꢀ Cp*IrCl2]+). IR(nujol): 2046 (CO),
˚
using Mo Ka radiation (k = 0.71069 A) at 0 °C under a
cold nitrogen stream. Four preliminary data frames were
measured at 0.5° increments of x, in order to assess the
crystal quality and preliminary unit cell parameters were
calculated. The cell parameters were refined using all the
reflections measured in the range 2.8° < 2h < 55.1°. The
intensity images were measured at 0.5° intervals of x or a
duration of 20 s. The frame data were integrated using a
d*TREK program package and the data sets were corrected
for absorption using a REQAB program. The crystal param-
eters along with data collections are summarized in Table
1.
841 (PF6) cmꢀ1
. d 1.27 (d,
1H NMR (CDCl3):
JPH = 2.5 Hz, Cp*, 15H), 1.68 (d, JPH = 2.5 Hz, Cp*,
15H), 4.60 (m, CH2, 1H), 5.11 (m, CH2, 1H), 6.9–7.7 (m,
Ph, 20H). 31P{1H} NMR(CDCl3):
JPP = 52.0 Hz), ꢀ11.2 (d, JPP = 52.0 Hz), ꢀ144.0 (sep.
JPF = 707 Hz, PF6). Anal. Calc. for C46H52OCl3F6P3Ir2:
C, 40.56; H, 3.95. Found: C, 40.59; H, 3.95%.
d
ꢀ1.62 (d,
Intensities were collected for Lorenz and polarization
effects. Atomic scattering factors were taken from the usual
tabulation of Cromer and Waber [13]. Anomalous disper-
sion effects were included in Fcalc [14]; the values of Df0
and Df00 were those of Creagh and McAuley [15]. All calcu-
lations were performed using the TEXSAN crystallographic
software package [16].
2.3.4. Preparation of [{Cp*IrCl(CO)2}2(dppb)](PF6)
(14b)
Yellow complex of 14b (53.0%) was obtained from
[(Cp*IrCl2)2(l-dppb)] (12b) (50.4 mg 0.041 mmol), phenyl-
acetylene (0.1 mL, 0.913 mmol), H2O (0.1 mL, 55 mmol)
and KPF6 (43.0 mg, 0.219 mmol) according to a procedure
similar to that of 8. The recrystallization was carried out
from CH2Cl2, methanol and diethyl ether. FAB mass:
m/z 1353 ([M + PF6]+). IR(nujol): 2052 (CO), 835 (PF6)
2.6. Determination of the structure
1
cmꢀ1. H NMR (CDCl3): d 1.29 (br, CH2, 4H), 1.67 (d,
The structures of 2b, 2c and 2e Æ Et2O were solved by
Patterson methods (DIRDIF92 PATTY) and refined on
F2 values for 2b and 2c, and on F values for 2e Æ Et2O.
The positions of all non-hydrogen atoms were refined with
JPH = 2.5 Hz, Cp*, 30H), 2.55 (m, CH2, 4H), 2.65 (m,
CH2, 4H), 7.4–7.7 (m, Ph, 20H). 31P{1H} NMR(CD2Cl2):
d ꢀ1.92 (s), ꢀ144.1 (sep. JPF = 707 Hz, PF6). Anal. Calc.

K. Ogata et al. / Inorganica Chimica Acta 359 (2006) 1549–1558
1553
Table 1
Crystal data for [Cp*Rh(PPh3){C(C6H4-4-Me)@CHCOCH2(C6H4-4-Me)}](PF6) 2b, [Cp*Rh(PPh3){C(C6H4-4-CO2Me)@CHCOCH2(C6H4-4-
CO2Me)}](PF6) 2c and [Cp*Rh(PMePh2) {C(Ph)@CHCOCH2Ph}](PF6) 2e Æ Et2O
Compound
2b
2c
2e Æ Et2O
Formula
C46H47OP2F6Rh
894.72
C48H47O5P2F6Rh
982.74
triclinic
C43H51O2P2F6Rh
878.72
Molecular weight
Crystal system
Space group
monoclinic
Pn (No. 7)
11.363(8)
9.32(1)
20.289(7)
90.0
103.06(4)
90.0
2093(2)
2
monoclinic
P21/c (No. 14)
10.840(2)
20.653(5)
18.956(3)
90.0
95.38(2)
90.0
4225(1)
4
ꢀ
P1 (No. 2)
˚
a (A)
9.530(2)
11.592(3)
20.716(4)
75.12(1)
83.834(2)
88.685(2)
2198.8(8)
2
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
˚
V (A)
Z
Dc (g cmꢀ3
)
1.419
5.45
1.484
5.32
1.381
5.40
l (Mo Ka) (cmꢀ1
)
Number of reflections
3690
9975
7428
(2h) (°)
Number of data used
(50.0)
3676
(55.1)
5192
(50.0)
4331
(I > 3.0r(I))
476
0.121; 0.180b
0.060(3285)
2.34
(I > 3.0r(I))
559
(I > 2.5r(I))
487
0.088; 0.175b
0.055(4331)
0.86
Number of variables
R:RW
R1 (reflections)
Goodness-of-fit (GOF)c
0.069; 0.081a
a,b
2.52
P
P
P
a
b
c
R = iFo| ꢀ |Fci/ |Fo| and Rw = [ w(|Fo| ꢀ |Fc|)2/w|Fo|2]1/2 (w = 1/r2(Fo)).
P
P
P
P
P
P
R = (F o2 ꢀ F 2c)/ F 2o and RW = [ w(F 2o ꢀ F c2)2/ w(F 2o)2]1/2 (w = 1/r2(Fo)); R1 = iFo| ꢀ |Fci/ |Fo| for I > 2.0r(I).
P
GOF = [ w(|Fo| ꢀ |Fc|2)/(No ꢀ Np)]1/2
.
anisotropic thermal parameters by using full-matrix least-
squares methods. All hydrogen atoms were calculated at
the ideal positions with the C–H distance of 0.95 A.
and 2d in the IR and 1H NMR measurements. It was deter-
mined by the X-ray analyses of 2b and 2c that the rhodium
atom is connected by triphenylphosphine, and the carbon
and carbonyl-oxygen atoms of the alkenyl ketone moiety
(Figs. 1, 2).
˚
3. Results and discussion
Reaction of 1 with 4-isocyanophenylacetylene afforded
3.1. Alkenyl ketone complexes of rhodium(III)
yellow complex
3
formulated as [Cp*RhCl(PPh3)-
(CNC6H4C„CH)](PF6) in high yield. The IR spectrum
showed characteristic bands at 3279 and 2174 cmꢀ1 in
addition to the presence of a PF6 anion at 843 cmꢀ1. The
former was assigned to an ethynyl moiety and the latter
to a terminal isocyanide. This spectral data suggested the
structure that a terminal carbon atom of isocyanide coordi-
nated the Rh metal, indicating strong coordination ability
of isocyanide.
Diphenylmethylphosphine complex 1e, Cp*RhCl2-
(PMePh2) reacted readily with phenylacetylene and H2O
in the presence of KPF6 to afford the alkenyl ketone com-
plex 2e in 61.5% yield, in which the structure was confirmed
by X-ray analysis (Fig. 3). A similar reaction with a binu-
clear dppm complex, [{Cp*RhCl2}2(l-dppm)] (4), generated
a Cl-bridged complex [{Cp*Rh(l-Cl)}2(l-dppm)](PF6)2(5)
without forming the corresponding alkenyl ketone complex
(Scheme 3).
On the treatment of Cp*RhCl2(PPh3) (1) with phenyl-
acetylene and H2O in the presence of KPF6 in CH2Cl2
and acetone at room temperature, orange crystals 2a were
obtained (Scheme 2).
Molecular peak of m/z = 721 in the FAB mass spec-
trometry and elementary analysis corresponded to the for-
mula of [Cp*Rh(PPh3)(PhC„CH)2(OH)](PF6). The
characteristic bands in the IR spectrum appeared at 1588
and 1547 cmꢀ1 due to a conjugated double bond in addi-
1
tion to a PF6 anion at 839 cmꢀ1. The H NMR spectrum
showed a doublet at 1.19 ppm due to Cp* protons and
an AB system centered at 3.25 ppm due to methylene pro-
tons. The 31P{1H} NMR spectrum showed a doublet at
38.0 ppm and a septet at ꢀ143.6 ppm assignable to PPh3
and PF6, respectively. Instead of KPF6, use of NaPF6 or
NH4PF6 also gave 2a. Other terminal alkynes such as p-
tolyl, 4-methoxycarbonylphenyl or 4-nitrophenyl acetylene
also generated the corresponding alkenyl ketone complexes
[Cp*Rh(PPh3){CR@CHCOCH2R}](PF6) (2 b: R = C6H4-
p-Me; 2c: R = C6H4-p-COOMe; 2d: R = C6H4-p-NO2).
Similar spectroscopic data were observed for the 2b, 2c
In some attempts to substitute the coordinated car-
bonyl-oxygen of alkenyl ketone or the coordinated triphe-
nylphosphine of 2a, the reactions with xylyl isocyanide,
P(OMe)3 or P(p-tolyl)3 were carried out and recovered
the starting complex of 80–91%. Complex 2a was treated

1554
K. Ogata et al. / Inorganica Chimica Acta 359 (2006) 1549–1558
+
R
L
a: Ph
b: p-tolyl
c: C6H4-p-COOMe PPh3
d: C6H4-p-NO2
e: Ph
PPh3
PPh3
HC CR
Rh
O
Ph3P
H2O, KPF6
C
C CH2R
R
PPh3
PPh2Me
C
H
Rh
Cl
Cl
L
2
+
1: L = PPh3
1e: L = PPh2Me
HC C6H4NC
H2O, KPF6
Rh
Cl
CNC6H4C CH
Ph3P
3
Scheme 2. Reactions of Cp*RhCl2(PPh3) with 1-alkynes and H2O in the presence of KPF6. The PF6 anions are omitted for clarity.
Fig. 1. ORTEP drawings for the complex cation of 2b; the PF6 anion and
hydrogen atoms are omitted for clarity and thermal ellipsoids are drawn to
encompass 50% probability.
Fig. 3. ORTEP drawings for the complex cation of 2e; the PF6 anion,
Et2O and hydrogen atoms are omitted for clarity and thermal ellipsoids
are drawn to encompass 50% probability.
2+
PPh2
Rh
Ph2P
Rh
HC CPh
Cl
[{Cp*RhCl2}2(dppm)]
H2O, KPF6
Cl
4
5
Scheme 3. Reactions of [{Cp*RhCl2}2(dppm)] with phenylacetylene and
H2O in the presence of KPF6. The PF6 anions are omitted for clarity.
3.2. The C–C triple bond-cleavage by iridium and ruthenium
complexes
Fig. 2. ORTEP drawings for the complex cation of 2c; the PF6 anion and
hydrogen atoms are omitted for clarity and thermal ellipsoids are drawn to
encompass 50% probability.
In some attempts to investigate whether the aforemen-
tioned reaction can be applicable for similar type of other
metal complexes, isoelectronic complexes such as
Cp*IrCl2(PPh3) (6) and (C6Me6)RuCl2(PPh3) (7) were
used. When 6 was treated with phenylacetylene, H2O and
KPF6 (or NaPF6), carbonyl complex 8 formulated as
[Cp*IrCl(PPh3)(CO)](PF6) from FAB mass spectrometry
with HBF4 at room temperature, generating [Cp*Rh-
(PPh3){CPh@CHCOCH2Ph}](BF4) by occurrence of an
anion-exchange. These reactions showed a high stability
of the five-membered ring structure and of the Rh–P bond.

K. Ogata et al. / Inorganica Chimica Acta 359 (2006) 1549–1558
1555
and elemental analysis, was obtained in 72.3% yield as a
yellow solid (Scheme 4).
doublets at 1.27 and 1.68 ppm consisting of a 1:1 ratio
for Cp* protons. The 31P{1H} NMR spectrum indicated
two doublets at ꢀ1.62 and ꢀ11.2 ppm with the coupling
The IR spectrum showed a band at 2049 cmꢀ1 due to a
terminal carbonyl group together with a band at 841 cmꢀ1
due to a PF6 anion. Similar reaction also occurred in ruthe-
nium complex 7, giving the corresponding carbonyl com-
2
constant JPP = 52.0 Hz in addition to a resonance at
ꢀ144.0 ppm due to the PF6 anions. These 1H and 31P
NMR data indicate the unsymmetrical structure of 13a.
In order to prepare a dicarbonyl complex of dppm, a fur-
ther reaction of 13a with phenyl acetylene and H2O was
carried out in the presence of KPF6, and 13a was recovered
quantitatively. No isolation of the dicarbonyl complex of
dppm is considered to result in electronic demand rather
than steric one, because carbonyl complex has been iso-
lated for the triphenylphosphine complex. The dppb com-
plex 12b afforded a pale yellow compound 14b. The IR
spectrum of 14b showed a CO stretching band at
2052 cmꢀ1. In the FAB mass spectrometry, the highest
value is m/z 1353, corresponding to the fragment of
[{Cp*IrCl(CO)}2(l-dppb) + PF6]+. The Cp* protons
plex
CpRuCl(PPh3)2
[(C6Me6)RuCl(PPh3)(CO)](PF6)
(9),
whereas
complex
afforded vinylidene
a
[CpRu(@C@CHPh)(PPh3)2](PF6) [17]. An origin of the
oxygen atom of carbonyl ligand had been confirmed to
be responsible for water. Thus, the reaction of
Cp*IrCl(MDMPP-P,O) with phenylacetylene was carried
out in the presence of H2 18O and gave [Cp*Ir(MDMPP-
P,O)(C18O)](PF6) in high yield [9]. The carbonyl stretching
frequency shifted from 2051 to 2004 cmꢀ1 in the IR spec-
trum. This shift was in good agreement with the calculated
value. In these reactions, saturated hydrocarbon with one
less carbon atom derived from cleavage of the C–C triple
bond of the terminal alkyne was detected by gas chromato-
1
appeared at 1.67 ppm as a doublet in the H NMR spec-
1
gram and H NMR spectrum. For example, toluene was
trum and the P nuclei of dppb appeared at ꢀ1.92 ppm as
a singlet in the 31P{1H} NMR spectrum. These data sug-
gested that 14b is a symmetrical dicarbonyl complex
[{Cp*IrCl(CO)}2(l-dppb)](PF6)2.
detected in case of the reaction of iridium complex 6 with
phenylacetylene, H2O and KPF6.
Reactions of binuclear iridium diphosphine complexes
[(Cp*IrCl2)2(l-Ph2P(CH2)nPPh2)] (12) (a: n = 1; b: n = 4)
under similar condition were carried out (Scheme 5). The
dppm complex 12a gave yellow crystals formulated as
[{Cp*IrCl(CO)}(Cp*IrCl2)(l-dppm)](PF6) (13a) from
FAB mass spectrometry. The IR spectrum showed a strong
3.3. Reaction pathway
In order to examine an origin of methylene protons in the
alkenyl ketone complexes, the reaction of 1 with phenyl-
acetylene and D2O took place in the presence of KPF6. In
1
band at 2046 cmꢀ1. The H NMR spectrum showed two
1
the H NMR spectrum, the methylene protons appeared
at 3.16 ppm as a broad signal, suggesting that one of the
methylene protons was incorporated from water (Scheme
6).
The reaction consists of an initial formation of a vinyl-
idene complex and a subsequent addition of H2O to pro-
duce a hydroxybenzyl carbene (Scheme 7). This process
was confirmed by the fact that in a separate experiment,
the tube reaction of a vinylidene complex [Cp*Rh-
Cl(PPh3){@C@CHPh}](PF6) with phenylacetylene in the
presence of H2O gave 2a. The next process proceeds with
+
HC CPh
M
M
+
C6H5CH3
H2O, NaPF6
Cl
CO
Ph3P
Ph3P
Cl
Cl
8: M = Ir (Cp*)
9: M = Ru (C6Me6)
6: M = Ir (Cp*)
7: M = Ru (C6Me6)
Scheme 4. Reactions of Cp*IrCl2(PPh3) or (C6Me6)RuCl2(PPh3) with
phenylacetylene and H2O in the presence of NaPF6. The PF6 anions are
omitted for clarity.
+
n = 1
Ir
Ir
Cl
CO
CH2
P
P
Cl
Cl
Ph2
Ph2
HC CPh
H2O, KPF6
13a
Ir
Ir
Cl
Cl
P (CH2)n
Ph2
P
Cl
Cl
2+
Ph2
n = 4
12 (a: n = 1; b: n = 4)
Ir
Ir
OC
CO
(CH2)4
P
P
Cl
Cl
Ph2
Ph2
14b
Scheme 5. Reactions of [{Cp*IrCl2}(diphos)] with phenylacetylene and H2O in the presence of KPF6. The PF6 anions are omitted for clarity.

1556
K. Ogata et al. / Inorganica Chimica Acta 359 (2006) 1549–1558
+
The oxygen atom of the carbonyl ligand was confirmed to
be generated from water by the separate experiment using
H2 18O as mentioned above.
Rh
HC CPh
O
Ph3P
It is a well-known reaction that the binary combination
of the 1-alkynes and water by iron-group metal complexes
lead to the cleavage of the C–C triple bond with formation
of CO and saturated hydrocarbon with one less carbon
atom [19]. Recently platinum- and iridium-assisted cleav-
age of the C–C triple bond by water has been documented
[20].
Cp*RhCl2(PPh3)
C
C CHDR
D2O, KPF6
R
C
H
Scheme 6. Reactions of Cp*RhCl2(PPh3) with phenylacetylene and D2O
in the presence of KPF6. The PF6 anions are omitted for clarity.
the insertion of another alkyne into the acyl-Rh intermedi-
ate derived from the elimination of an H+ ion, followed by
an intramolecular coordination of the acyl oxygen atom to
the Rh metal. The acyl intermediate was assumed from the
fact that transformation of a hydroxycarbene complex to
an acyl one has been cited in several instances [18]. An
insertion of 1-alkyne into an acyl complex has also been
documented [4].
In the iridium and ruthenium complexes the C–C bond-
cleavage from the hydroxycarbene complex occurred to
form the carbonyl complex and toluene derivative. The tol-
uene derivative was detected by 1H NMR and GC analysis.
3.4. Molecular structures
Crystal structures of 2b, 2c and 2e: Perspective drawings
of 2b, 2c and 2e with the atomic numbering scheme are
given in Figs. 1–3 and selected bond lengths and angles
are listed in Tables 2–4.
The molecules have the piano-stool structures. The rho-
dium atom is surrounded by tertiary phosphine and a five-
membered ring derived from coordination of the carbon
and carbonyl-oxygen atoms of the alkenyl ketone moiety.
The average C–Rh–O bite angle and P–Rh–C bond angle
are 79.1° and 93.1°, respectively. The P–Rh–O angles are
+
+
-
H2O
HC CR / PF6
M
M
CH2R
M
Ph3P
C
Ph3P
Cl
Cl
C
Ph3P
R
C
Cl
Cl
OH
Cl-
H
M = Rh, Ir or Ru
RCH3
M = Rh
M = Ir, Ru
H+
Cp* for Rh, Ir
C6Me6 for Ru
:
+
Rh
CH2R
Ph3P
Cl-
C
O
Cl
M
Ph3P
CO
Cl
HC CR
+
+
Rh
Rh
C
Ph3P
RC
O
Ph3P
R
O
C
C
CH2R
C
CH2R
CH
H
Scheme 7. Possible pathway for the formation of the alkenyl ketone and carbonyl complexes. The PF6 anions are omitted for clarity.
Table 2
Selected bond lengths and angles for [Cp*Rh(PPh3){C(C6H4-4-Me)@CHCOCH2 (C6H4-4-Me)}] (PF6) (2b)
Rh(1)–P(1)
C(11)–C(19)
2.339(3)
1.42(2)
Rh(1)–O(1)
C(19)–C(20)
2.102(8)
1.39(2)
Rh(1)–C(11)
O(1)–C(20)
2.01(1)
1.26(1)
P(1)–Rh(1)–C(11)
Rh(1)–C(11)–C(19)
O(1)–C(20)–C(19)
93.5(4)
110.7(8)
119(1)
O(1)–Rh(1)–C(11)
C(11)–C(19)–C(20)
O(1)–C(20)–C(21)
80.4(4)
116(1)
115(1)
P(1)–Rh(1)–O(1)
Rh(1)–O(1)–C(20)
86.4(2)
111.6(8)

K. Ogata et al. / Inorganica Chimica Acta 359 (2006) 1549–1558
1557
Table 3
Selected bond lengths and angles for [Cp*Rh(PPh3){C(C6H4-4-COOMe)@CHCOCH2(C6H4ꢀ4-COOMe)}](PF6) (2c)
Rh(1)–P(1)
O(1)–C(3)
2.355(2)
1.251(9)
Rh(1)–O(1)
C(1)–C(2)
2.113(5)
1.37(1)
Rh(1)–C(1)
C(2)–C(3)
2.016(6)
1.43(1)
P(1)–Rh(1)–C(1)
Rh(1)–C(1)–C(2)
O(1)–C(3)–C(2)
93.3(2)
113.5(6)
119.0(7)
O(1)–Rh(1)–C(1)
C(1)–C(2)–C(3)
O(1)–C(3)–C(4)
79.0(3)
115.4(7)
119.4(7)
P(1)–Rh(1)–O(1)
Rh(1)–O(1)–C(3)
85.0(1)
113.0(5)
Table 4
Selected bond lengths and angles for [Cp*Rh(PPh2Me){C(Ph)@CHCOCH2Ph}](PF6) (2e)
Rh(1)–P(1)
O(1)–C(13)
2.314(2)
1.274(7)
Rh(1)–O(1)
C(11)–C(12)
2.091(4)
1.370(9)
Rh(1)–C(11)
C(12)–C(13)
2.027(6)
1.399(9)
P(1)–Rh(1)–C(11)
Rh(1)–C(11)–C(12)
O(1)–C(13)–C(12)
92.6(2)
113.5(5)
118.6(5)
O(1)–Rh(1)–C(11)
C(11)–C(12)–C(13)
O(1)–C(13)–C(14)
78.6(2)
115.8(5)
116.9(6)
P(1)–Rh(1)–O(1)
Rh(1)–O(1)–C(13)
89.0(1)
113.5(4)
89.0(1)°, 86.4(2)° and 85.0(1)° for 2e, 2b and 2c, respec-
5. Supplementary material
tively. This trend was traced back to a decrease of the
˚
Rh–P bond lengths: 2.313(2), 2.339(3) and 2.355(2) A for
CCDC numbers: 163783 for 2b, 211504 for 2c and
211505 for 2e. Copies of this information can be obtained
free of charge from The Director, CCDC, 12, Union Road,
Cambridge CB2 1EZ, UK (fax: +44 1223 336033; e-mail:
deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk).
2e, 2b and 2c, respectively, resulting in release of steric
interaction of tertiary phosphine ligand. The C–O and C–
˚
C double bond lengths are 1.26 and 1.38 A, respectively,
not significantly different from the corresponding usual
values.
The Rh–O coordinated bond lengths are in the range
Acknowledgements
˚
˚
from 2.091 to 2.113 A, longer than those (2.050–2.08 A)
found in the Rh–O r-bond lengths of the neutral or ionic
complexes such as Cp*RhCl(MDMPP-P,O) [21], Cp*RhCl-
(BDMPP-P,O) [8] and [Cp*Rh(BDMPP-P,O)(CO)](PF6)
(BDMPP-P,O = PPh{C6H3-2,6-(MeO)2}(C6H3-2-O-6-MeO))
[21]. This trend results in the difference of the bonding
modes.
The authors thank Professor Shigetoshi Takahashi and
Dr. Fumie Takei of The Institute of Scientific and Indus-
trial Research, Osaka University, for performing the
FAB mass spectrometry measurements. This work was
partially supported by a Grant-in Aid for Scientific Re-
search from the Ministry of Education, Science, Culture
and Sports, Japan.
4. Conclusion
References
This paper provides difference on reactivity between
rhodium and iridium complexes. Thus it reports a conve-
nient one-pot synthesis of alkenyl ketone complexes from
simple pentamethylcyclopentadienyl rhodium(III) com-
plex, 1-alkyne and H2O in the presence of KPF6. In irid-
ium(III) and ruthenium(II) complexes, a C–C triple
bond-cleavage of the 1-alkyne occurred readily, generating
carbonyl complex and saturated hydrocarbon with one less
carbon atom. Since double insertion of 1-alkyne into the
Rh–O bonds has been documented [7,8], rhodium com-
plexes may be expected as the precursors for metal-assisted
multiple insertion of 1-alkynes. The C–C triple bond-cleav-
age reactions have been well-known in ruthenium com-
plexes [19]. Iridium complexes may be candidates for a
catalyst of the C–C multiple bond-cleavage. There is no
evidence to explain the different reactivities between rho-
dium and iridium complexes, but tendency for the C–C tri-
ple bond-cleavage assisted by the rhodium complexes is
more effective than that by the iridium complexes. The sim-
ilar trend has been observed in the reactions of the P,O-
chelate complexes with 1-alkyne as shown in Scheme 1.
[1] (a) M. Ryang, Y. Sawa, S.N. Somasundaram, S. Murai, S. Tsutsumi,
J. Organomet. Chem. 46 (1972) 375;
(b) P. Deshong, D.R. Sidler, P.J. Rybczynski, G.A. Slough, A.L.
Rheinghold, J. Am. Chem. Soc. 110 (1988) 2575;
(c) A.B. Smith III, P.A. Levenberg, P.J. Jerris, R.M. Scarborough
Jr., P.M. Wovkulich, J. Am. Chem. Soc. 103 (1981) 101.
´
[2] J. Barluenga, J.R. Fernandez, M. Yus, J. Chem. Soc., Chem.
Commun. (1986) 183, and references therein.
´
´
[3] E. Carmona, E. Gutierrez-Puebla, A. Monge, J.M. Marın, M.
Paneque, M.L. Poveda, Organometallics 8 (1989) 967.
[4] (a) H.G. Alt, M.E. Eichner, B.M. Jansen, Angew. Chem., Int. Ed.
Engl. 21 (1982) 861;
(b) H.G. Alt, U. Thewalt, J. Organomet. Chem. 268 (1984) 235;
(c) H.G. Alt, J. Organomet. Chem. 288 (1985) 149;
(d) H.G. Alt, H.E. Engelhardt, U. Thewalt, J. Riede, J. Organomet.
Chem. 288 (1985) 165;
(e) H.G. Alt, H.I. Hayen, J. Organomet. Chem. 315 (1986) 337.
´
[5] A. Elarraoui, J. Ros, R. Yanez, X. Solans, M. F-Bardia, J.
˜
Organomet. Chem. 642 (2002) 107.
[6] Y. Yamamoto, J. Seta, H. Murooka, X.-H. Han, Inorg. Chem.
Commun. 6 (2003) 202.
[7] (a) Y. Yamamoto, X.-H. Han, J.-F. Ma, Angew. Chem., Int. Ed. 39
(2000) 196;

1558
K. Ogata et al. / Inorganica Chimica Acta 359 (2006) 1549–1558
´
´
(b) Y. Yamamoto, K. Sugawara, J. Chem. Soc., Dalton Trans. (2000)
(e) C. Menendez, D. Morales, J. Perez, V. Riera, D. Miguel,
2896;
Organometallics 20 (2001) 2775.
(c) Y. Yamamoto, K. Sugawara, M. Kakeya, Inorg. Chim. Acta 340
(2002) 21.
[19] (a) C. Bianchini, J.A. Casares, M.A. Peruzzini, A. Romerosa, F.
Zanobini, J. Am. Chem. Soc. 118 (1996) 4585;
[8] Y. Yamamoto, K. Sugawara, X.-H. Han, J. Chem. Soc., Dalton
Trans. (2002) 195.
[9] K. Ogata, K. Kuge, K. Tatsumi, Y. Yamamoto, J. Chem. Soc.,
Chem. Commun. (2002) 128.
(b) W. Knaup, H. Werner, J. Organomet. Chem. 411 (1991) 471;
(c) M.I. Bruce, A.G. Swincer, Aust. J. Chem. 32 (1979) 1471;
(d) O.M. Abu Salah, M.I. Bruce, J. Chem. Soc, Dalton Trans. (1974)
2302;
[10] J.W. Kang, K. Moseley, P.M. Maitlis, J. Am. Chem. Soc. 91 (1969)
5970.
[11] M.A. Bennett, A.K. Smith, J. Chem. Soc., Dalton Trans. (1974)
233.
[12] W. Keim, P. Kraneburg, G. Dahmen, G. Deckers, Organometallics
13 (1994) 3085.
[13] D.T. Cromer, J.T. Waber, International Tables for X-ray Crystal-
lography, Kynoch, Birmingham (England), 1974, Table 2.2A.
[14] J.A. Ibers, W.C. Hamilton, Acta Crystallogr. 17 (1964) 718.
[15] D.C. Creagh, W.J. McAulley, International Tables for Crystallogra-
phy, vol. C, Kluwer, Boston, 1992, Table 4.2.6.8, pp. 219–222.
[16] TEXSAN: Crystal Structure Analysis Package, Molecular Structure
Corporation Houston, TX, 1985 and 1992.
(e) M.I. Bruce, Pure Appl. Chem. 58 (1986) 553;
(f) B.P. Sullivan, R.S. Smythe, E.M. Kober, T.J. Meyer, J. Am.
Chem. Soc. 104 (1982) 4701;
(g) C. Mountassir, T.B. Harada, H. Le Bozec, J. Organomet. Chem.
388 (1990) C13;
(h) S. Davies, J.P. McNally, A.J. Smallridge, Adv. Organomet.
Chem. 30 (1990) 30;
(i) C. Bianchini, M.A. Peruzzini, F. Zanobini, C.E. Lopez, I. de los
Rios, A. Romerosa, J. Chem. Soc., Chem. Commun. (1999) 443;
(j) C. Bianchini, I. de los Rios, C. Lopez, M. Peruzzini, A. Romerosa,
J. Organomet. Chem. 593–594 (2000) 485.
[20] (a) U. Belluco, R. Bertani, F. Meneghetti, R.A. Michelin, M.
Mozzon, J. Organomet. Chem. 583 (1999) 131;
[17] S. Takahashi, private communication.
[18] (a) M.I. Bruce, Chem. Rev. 91 (1991) 187;
(b) J.M. O’Connor, K. Hiibner, J. Chem. Soc., Chem. Commun.
(1995) 1209;
(b) M.I. Bruce, Chem. Rev. 98 (1998) 2797;
(c) C.S. Chin, D. Chong, B. Maeng, J. Ryu, H. Kim, M. Kim, H.
Lee, Organometallics 21 (2002) 1739;
(d) G. Albertin, S. Antoniutti, A. Bacchi, G. Pelizzi, F. Piasente,
Dalton Trans. (2003) 2881.
(c) C. Bruneaau, P.H. Dixneuf, Acc. Chem. Rev. 32 (1999) 311;
(d) F.A. Hill, in: E. w. Abel, F.G.A. Stone, G. Wilkinson (Eds.),
Comprehensive Organometallic Chemistry II, vol. 7, Pergamonress,
Oxford, UK, 1995, p. 351;
[21] X.-H. Han, Y. Yamamoto, J. Organomet. Chem. 561 (1998) 157.