One-pot syntheses of alkenyl-phosphonio complexes of ruthenium(II), rhodium(III) and iridium(III) bearing p-cymene or pentamethylcyclopentadienyl groups

Article abstract of DOI:10.1016/j.ica.2007.03.053

Reaction of [(p-cymene)RuCl₂(PPh₃)] (1) or [Cp^*MCl₂(PPh₃)] (Cp^* = C₅Me₅) (3a: M = Rh; 4a: M = Ir) with 1-alkynes and PPh₃ were carried out in the presence o

Full text of DOI:10.1016/j.ica.2007.03.053

Inorganica Chimica Acta 360 (2007) 3296–3303
www.elsevier.com/locate/ica
One-pot syntheses of alkenyl-phosphonio complexes
of ruthenium(II), rhodium(III) and iridium(III) bearing p-cymene
or pentamethylcyclopentadienyl groups
a,
a
a
b
Kenichi Ogata *, Jyoji Seta , Yasuhiro Yamamoto , Katsuaki Kuge ,
b,1
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 8 December 2006; received in revised form 20 March 2007; accepted 31 March 2007
Available online 11 April 2007
Abstract
Reaction of [(p-cymene)RuCl2(PPh3)] (1) or [Cp*MCl2(PPh3)] (Cp* = C5Me5) (3a: M = Rh; 4a: M = Ir) with 1-alkynes and PPh3 were
carried out in the presence of KPF6, generating the corresponding alkenyl-phosphonio complexes, [(p-cymene)RuCl(PPh3)-
{CH@CR(PPh3)}](PF6) (2a: R = Ph; 2b: R = p-tolyl) or [Cp*MCl(PPh3){CH@CPh(PPh3)}](PF6) (5: M = Rh; 6: M = Ir). Similar reac-
tions of complexes [Cp*RhCl2(L1)] (3a: L1 = PPh3; 3c: L1 = P(OMe)3) with L2 (L2 = PPh3, PMePh2, P(OMe)3) gave
[Cp*RhCl(L1)(L2)](PF6) (7bb: L1 = L2 = PMePh2; 7ca: L1 = P(OMe)3, L2 = PPh3; 7cc: L1 = L2 = P(OMe)3). Alkenyl-phosphonio com-
plex 5 was treated with P(OMe)3 or 2,6-xylyl isocyanide, affording [Cp*RhCl(L){CH@CPh(PPh3)}] (PF6) (8a: L = P(OMe)3; 8b: L = 2,6-
xylNC). X-ray structural analyses of 2a, 6 and 8a revealed that the phosphonium moiety bonded to the Cb atom of the alkenyl group are
E configuration.
Ó 2007 Elsevier B.V. All rights reserved.
Keywords: Ruthenium complex; Rhodium complex; Iridium complex; Alkenyl-phosphonio complex; Alkyne
1. Introduction
ence of KPF6 gave alkenyl-ketone derivative, [Cp*RhCl
(PPh3){CPh@CHCOCH2Ph}](PF6) with a (C,O) chelated
group, constructed by two alkynes and a hydroxyl group
[2]. In an iridium complex, the reaction was accompanied
by the cleavage of the C–C triple bond of phenylacetylene
to afford [Cp*IrCl(CO)(PPh3)](PF6) and toluene with one
less carbon atom. These reactions proceeded through a
vinylidene intermediate.
The chemistry of metal vinylidene complexes has experi-
enced important developments due to the discovery of con-
venient synthetic methodologies and their involvement in
selective catalytic transformation of 1-alkynes [1].
We have reported that the reaction of [Cp*RhCl2(PPh3)]
(Cp* = C5Me5) with phenylacetylene and H2O in the pres-
We report here that when triphenylphosphine instead of
H2O was used as nucleophile, alkenyl-phosphonio com-
plexes were generated readily and selectively. In regard to
our research, Gimeno and his coworkers have reported
that the reactions of indenyl–ruthenium(II) complexes
[(C9H7)Ru{=C@CH(cyclo-C@CHCH2(CH2)nCH2) (PPh3)2]
(BF4) (n = 1,2) with a large excess of PPh3 in refluxing
methanol yields alkenyl-phosphonio derivatives [3].
*
Corresponding author. Present address: Department of Organic and
Polymer Materials Chemistry, Tokyo University of Agriculture and
Technology, 2-24-26 Naka-cho, Koganei-shi, Tokyo 184-8588, Japan.
Tel./fax: +81 42 388 7162.
E-mail addresses: kogata@cc.tuat.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 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2007.03.053

K. Ogata et al. / Inorganica Chimica Acta 360 (2007) 3296–3303
3297
Recently they have reported that the addition of triphenyl-
JHH = 6.0 Hz, p-cymene), 7.0–7.8 (m, 35H, Ph), 9.63
(dd, 1H, 3JP1H = 32.5 Hz, 3JP2H = 20.5 Hz, @CH).
31P{1H} NMR (CDCl3): d 25.8 (s, PPh3), 18.9 (s, PPh3),
ꢀ143.5 (sep, JPF = 712 Hz, PF6). Anal. Calc. for
C54H50P3ClF6Ru Æ C4H5O: C, 62.39; H, 5.42. Found: C,
62.71; H, 5.36%.
phosphine to a transient p-alkyne species arising from
i
[(1,2,3-Me3C9H4)RuBr(CO)(PR3)] (R = Ph, Pr), phenyl-
acetylene and AgBF4 also gave [(1,2,3-Me3C9H4)Ru-
{CH@C(PPh3)Ph}(CO)(PR3)] (PF6) [4]. As for iridium
complexes, several workers have reported that several iridium
alkenyl-phosphonio complexes [IrR(CH@CH+PPh3)2
(CO)(PPh)3]2+ (R = H, CH3, Cl) and [IrBr(R)(CH@
CH+PPh3)2(CO)(PPh3)]+ (R = CH3, Br) were generated
from the reaction of iridium complex is with acetylene
and triphenylphosphine at room temperature [5].
In this article, we report a synthesis of alkenyl-phospho-
nio complexes. A part of this work has already been pub-
lished [6].
2.2.2. Preparation of [(p-cymene)RuCl(PPh3){CH@C
(p-tolyl)(PPh3)}](PF6) (2b)
Yellow crystals of 2b (70.3 mg, 40.4%) were obtained
from [(p-cymene)RuCl2(PPh3)] (1) (93.7 mg, 0.165 mmol),
KPF6 (90.4 mg, 0.491 mmol), PPh3 (138.2 mg, 0.527
mmol) and p-tolylacetylene (0.1 mL, 0.8 mmol) according
to a procedure similar to that of 2a. IR (nujol): 837
1
(PF6) cmꢀ1. H NMR (CDCl3): d 0.92 (d, JHH = 7.0 Hz,
i
i
2. Experimental
3H, Pr-CH3), 1.02 (d, JHH = 7.0 Hz, 3H, Pr-CH3), 1.70
i
(s, 3H, CH3), 2.07 (sep, JHH = 7.0 Hz, 1H, Pr-CH), 2.34
2.1. General procedures
(s, 3H, CH3), 4.01 (d, JHH = 6.0 Hz, 1H p-cymene), 4.18
(d, JHH = 6.0 Hz, 1H, p-cymene), 5.26 (d, JHH = 6.0 Hz,
2H, p-cymene), 7.0–7.8 (m, 34H, Ph), 9.61 (dd,
All manipulations were carried out under a nitrogen
atmosphere. Dichloromethane was distilled over CaH2
and diethyl ether was distilled over LiAlH4. (p-Cym-
ene)RuCl2(PPh3) (1) [7], Cp*RhCl2(PPh3) (3a) [8],
Cp*RhCl2(P(OMe)3) (3c) [8], Cp*IrCl2(PPh3) (4a) [8],
[(Cp*RhCl2)2(l-dppp)] (9a) [9] and [(Cp*RhCl2)2(l-dppm)]
(9b) [9] were prepared according to the literature methods.
Other reagents employed in this research were commer-
cially available and were used without further
purification. The infrared spectra were measured on FT/
IR-5300. The 1H 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 bom-
bardment (FAB) mass spectra were measured on a JMS-
DX300 spectrometer. Elementary analyses were per-
formed by Analytical Center, School of Pharmaceutical
Science, Toho University.
3
3JP1H = 32.8 Hz, JP2H = 20.5 Hz, 1H, @CH). 31P{1H}
NMR (CDCl3): d 37.4 (s, PPh3), 18.6 (s, PPh3), ꢀ143.5
(sep,
JPF = 712 Hz,
PF6).
Anal.
Calc.
for
C55H52P3ClF6Ru: C, 62.53; H, 4.96. Found: C, 62.83;
H, 5.14%.
2.2.3. Preparation of [(Cp*RhCl(PPh3)
{CH@CPh(PPh3)})](PF6) (5)
Yellow crystals of 5 (101 mg, 81.5%) were obtained
from [Cp*RhCl2(PPh3)] (3a) (67.9 mg, 0.119 mmol),
KPF6
(38.0 mg,
0.207 mmol),
PPh3
(69.6 mg,
0.265 mmol) and phenylacetylene (0.1 mL, 0.8 mmol)
according to a procedure similar to that of 2a. IR
(nujol): 839 (PF6) cmꢀ1 1H NMR (CDCl3): d 1.08 (d,
.
JHH = 3.4 Hz, 15H, Cp*), 6.7–7.8 (m, 30H, Ph), 9.69
3
3
(ddd, JP1H = 34.8 Hz, JP2H = 21.1 Hz, JRhH = 3.0 Hz,
1H, @CH). 31P{1H} NMR (CDCl3):
d
36.8 (d,
JRhP = 156 Hz, PPh3), 21.5 (d, JRhP = 16.2 Hz, PPh),
ꢀ143.5 (sep, JPF = 713 Hz, PF6). Anal. Calc. for
C50H51P3ClF6Rh: C, 62.05; H, 4.92. Found: C, 61.77;
H, 5.14%.
2.2. Preparation of alkenyl-phosphonio complexes
2.2.1. Preparation of [(p-cymene)RuCl(PPh3)
{CH@CPh(PPh3)}](PF6) (2a)
To
a
mixture of [(p-cymene)RuCl2(PPh3)] (1)
(111.8 mg, 0.197 mmol), KPF6 (83.1 mg, 0.495 mmol)
and PPh3 (112.2 mg, 0.428 mmol) in CH2Cl2 (10 mL)
and acetone (15 mL), phenyl acetylene (0.1 mL, 0.9 mmol)
was added. After stirring for 4 h at room temperature, the
solvent was removed. The residue was washed with
diethyl ether. After the residue was extracted with
CH2Cl2, the filtrate was concentrated and was recrystal-
lized from CH2Cl2 and diethyl ether, giving yellow crys-
2.2.4. Preparation of [(Cp*IrCl(PPh3)
{CH@CPh(PPh3)})](PF6) (6)
Yellow crystals of 6 (60.6 mg, 35.1%) were obtained
from [Cp*IrCl2(PPh3)] (4a) (100.5 mg, 0.152 mmol),
KPF6 (56.3 mg, 0.306 mmol), PPh3 (58.3 mg, 0.222 mmol)
and phenylacetylene (0.1 mL, 0.8 mmol) according to a
procedure similar to that of 2a. IR (nujol): 839
(PF6) cmꢀ1. FAB mass: m/z = 989 ([Mꢀ1]+). 1H NMR
(CDCl3): d 1.08 (d, JHH = 2.2 Hz, 15H, Cp*), 6.7–7.8
tals of 2a (96.0 mg, 43.9%). IR (nujol): 833 (PF6) cmꢀ1
.
3
3
FAB mass: m/z = 898 ([M+1]+). 1H NMR (CDCl3): d
0.91 (d, JHH = 7.0 Hz, 3H, CH3), 1.02 (d, JHH = 7.0 Hz,
(m, 30H, Ph), 10.36 (dd, JP1H = 34.7 Hz, JP2H =
18.2 Hz, 1H, @CH). 31P{1H} NMR (CDCl3): d 25.8 (s,
PPh3), 4.09 (s, PPh3), ꢀ143.5 (sep, JPF = 712 Hz, PF6).
Anal. Calc. for C50H51P3ClF6Ir: C, 57.17; H, 4.53.
Found: C, 57.47; H, 4.68%.
i
3H, Pr-CH3), 1.67 (s, 3H, CH3), 2.07 (sep, JHH = 7.0 Hz,
i
1H, Pr-CH), 4.02 (d, JHH = 6.0 Hz, 1H, p-cymene), 4.18
(d, 1H, JHH = 6.0 Hz, p-cymene), 5.26 (t, 2H,

3298
K. Ogata et al. / Inorganica Chimica Acta 360 (2007) 3296–3303
2.3. Formation of [Cp*RhClL2](PF6) (L = phosphine or
phosphite) complexes
3JP1H = 33.1 Hz,3JP2H = 4.8 Hz,
CH=). 31P{1H} NMR (CDCl3): d 124.0 (dd, JRhP
JRhH = 4.4 Hz,
1H,
=
240 Hz, JPP = 8.0 Hz, P(OMe)3), 19.4 (dd, JRhP = 10.6 Hz,
JPP = 8.0 Hz, PPh3), ꢀ143.6 (sep, JPF = 712 Hz, PF6).
Anal. Calc. for C39H45P3O3ClF6Rh: C, 51.64; H, 5.00.
Found: C, 51.55; H, 4.93%.
2.3.1. Formation of [Cp*RhCl(PMePh2)2](PF6) (7bb)
Yellow crystals of 7bb (59.3 mg, 49.5%) were obtained
from [(Cp*RhCl2](PPh3)) (3a) (83.6 mg, 0.146 mmol),
KPF6 (53.2 mg, 0.289 mmol), PMePh2 (0.2 mL, 1.07 mmol)
and phenylacetylene (0.1 mL, 0.8 mmol) according to a
2.4.2. Preparation of
procedure similar to that of 2a. IR (nujol): 839 (PF6) cmꢀ1
.
[Cp*RhCl(CNXyl){CH@CPh(PPh3)}](PF6) (8b)
Yellow crystals of 8b (39.7 mg, 71.7%) were obtained
from [Cp*RhCl(PPh3){CH@ CPh(PPh3)}](PF6) (5)
(63.3 mg, 0.0606 mmol), and xylyl isocyanide (27.6 mg,
0.211 mmol) according to a procedure similar to that of
8a. IR (nujol): 2162 (C„N), 839 (PF6) cmꢀ1. FAB mass:
1H NMR (CDCl3): d 1.30 (t, JPH = 3.5 Hz, 15H, Cp*), 1.45
(t, JPH = JRhH = 5.1 Hz, P(CH3), 6 H), 7.0–7.8 (m, 20H,
Ph). 31P{1H} NMR (CDCl3): d 13.5 (d, JRhP = 136 Hz,
PMePh2), ꢀ143.8 (sep, JPF = 712 Hz, PF6). Anal. Calc.
for C36H41P3ClF6Rh: C, 52.80; H, 5.05. Found: C, 52.82;
H, 5.11%.
1
m/z = 666 ([M+1]+). H NMR (CDCl3): d 1.63 (s, 15H,
Cp*), 2.15 (s, 6H, CH3), 6.5–7.8 (m, 33H, Ph), 9.15 (dd,
3
2.3.2. Formation of [Cp*RhCl(P(OMe)3)(PPh3)](PF6)
(7ca)
3JP1H = 29.4 Hz, JP2H = 5.3 Hz, 1H, CH=). 31P{1H}
NMR (CDCl3): d 19.2 (d, JRhP = 9.5 Hz, PPh3), ꢀ143.6
(sep, JPF = 712 Hz, PF6). Anal. Calc. for C45H47NClP2-
F6Rh: C, 58.99; H, 5.17; N, 1.53. Found: C, 58.55; H,
4.99; N, 1.43%.
Yellow crystals of 7ca (109.9 mg, 68.0%) were obtained
from [Cp*RhCl2(P(OMe)3)] (3c) (87.0 mg, 0.212 mmol),
KPF6 (64.3 mg, 0.349 mmol), PPh3 (71.9 mg, 0.274 mmol)
and phenylacetylene (0.1 mL, 0.8 mmol) according to a
procedure similar to that of 2a. IR (nujol): 839 (PF6) cmꢀ1
.
2.5. Reaction of binuclear rhodium complexes with alkyne
and triphenylphosphine
1H NMR (CDCl3): d 1.41 (dd, JPH = 5.7 Hz, 15H, Cp*),
3.67 (d, JPH = 11.0 Hz, 3H, P(OMe)3), 7.3–7.7 (m, 15H,
Ph). 31P{1H} NMR (CDCl3): d 2.30 (dd, JRhP = 132 Hz,
JPP = 91.8 Hz, PPh3), 110.8 (dd, JRhP = 217 Hz,
JPP = 91.8 Hz, P(OMe)3), ꢀ143.8 (sep, JPF = 712 Hz, PF6).
Anal. Calc. for C31H39P3O3ClF6Rh: C, 46.26; H, 4.88.
Found: C, 46.55; H, 4.85%.
2.5.1. Formation of [{Cp*RhCl(PPh3)}2(dppp)](PF6)2
(10)
A
mixture of [(Cp*RhCl2)2(dppp)] (9a) (53.5 mg,
0.052 mmol), KPF6 (32.5 mg, 0.18 mmol), PPh3 (47.0 mg,
0.18 mmol) and phenylacetylene (0.2 mL, 1.6 mmol) in
CH2Cl2 (10 mL) and acetone (10 mL) was stirred for 12 h
at room temperature and the solvent was removed and
the residue was extracted with CH2Cl2. The filtrate was
concentrated and diethyl ether was added, giving orange
2.3.3. Formation of [Cp*RhCl(P(OMe)3)2](PF6) (7cc)
Yellow crystals of 7cc (50.4 mg, 47.7%) were obtained
from [Cp*RhCl2(PPh3)] (3a) (90.6 mg, 0.159 mmol), KPF6
(56.7 mg, 0.308 mmol), P(OMe)3 (0.2 mL, 1.70 mmol)
and phenylacetylene (0.1 mL, 0.8 mmol) according to a
crystals of 10 (39.6 mg, 43.0%). IR (nujol): 839 (PF6) cmꢀ1
.
1H NMR (CD3COCD3): d 1.23 (t, JPH = JRhH = 3.2 Hz,
30H, Cp*), 2.07 (m, 2H, CH2), 2.78 (m, 4H, CH2), 7.5–
7.7 (m, 50H, Ph). 31P{1H} NMR (CDCl3): d 27.3 (dd,
JRhP = 138.7 Hz, JPP = 51.0 Hz, PPh3), 19.3 (dd,
JRhP = 133.8 Hz, JPP = 51.0 Hz, PPh3), ꢀ143.6 (sep,
JPF = 707 Hz, PF6). Anal. Calc. for C83H86Cl2P6F13Rh2.
0.5CH2Cl2: C, 55.21; H, 4.83. Found: C, 55.05; H, 5.10%.
procedure similar to that of 2a. IR (nujol): 837 (PF6) cmꢀ1
.
1H NMR (CDCl3): d 1.74 (t, JPH = 5.4 Hz, 15H, Cp*),
3.87 (t, JPH = JRhH = 5.1 Hz, 6H, P(OMe)3). 31P{1H}
NMR (CDCl3): d 117.5 (d, JRhP = 211 Hz, P(OMe)3),
ꢀ143.8 (sep, JPF = 712 Hz, PF6). Anal. Calc. for
C16H33P3O6ClF6Rh: C, 28.82; H, 4.99. Found: C, 29.12;
H, 4.99%.
2.5.2. Formation of [Cp*RhCl(PPh3)
2.4. Reaction of alkenyl-phosphonio complexes
{CH@CPh(PPh3)}](PF6) (5a) and
[Cp*RhCl(dppm)](PF6) (11)
2.4.1. Preparation of [Cp*RhCl(P(OCH3)3)
{CH@CPh(PPh3)}](PF6) (8a)
A mixture of [(Cp*RhCl2)2(l-dppm)] (9b) (46.0 mg,
0.046 mmol), KPF6 (53.3 mg, 0.29 mmol), PPh3 (65.7 mg,
0.25 mmol) and phenylacetylene (0.2 mL, 1.6 mmol) was
stirred in CH2Cl2 (10 mL) and acetone (10 mL) at room
temperature. After 18 h, the solvent was removed and the
residue was extracted with CH2Cl2. The solution was con-
centrated and diethyl ether was added, giving yellow pow-
der of 11 (34.4 mg, 46.7%). The mother liquor was
concentrated and diethyl ether was added, giving orange
crystals of 5a (26.6 mg, 27.8%). 11: FAB mass: m/z = 657
A mixture of [Cp*RhCl(PPh3){CH@ CPh(PPh3)}](PF6)
(5) (38.7 mg, 0.0370 mmol) and trimethylphosphite
(0.1 mL, 0.85 mmol) in CH2Cl2 (10 mL) was stirred at
room temperature. After 24 h, the solution was concen-
trated and was recrystallized from CH2Cl2 and diethyl
ether, giving a yellow crystals of 8a (17.5 mg, 52.1%). IR
(nujol): 837 (PF6) cmꢀ1 1H NMR (CDCl3): d 1.44 (d,
.
JPH = 4.8 Hz, 15H, Cp*), 3.73 (d, JPH = 11.2 Hz, 9H,
P(OMe)3), 6.9–7.9 (m, 15H, Ph), 9.80 (ddd,
([Mꢀ1]+), 625 ([MꢀClꢀ1]+). IR(nujol): 839 (PF6) cmꢀ1
.

K. Ogata et al. / Inorganica Chimica Acta 360 (2007) 3296–3303
3299
1H NMR (CDCl3): d 1.75 (t, JPH = 4.0 Hz, 15H, Cp*), 4.47
(b, 2H, CH2), 7.3–7.6 (m, 20H, Ph). 31P{1H} MNR
(CDCl3): d ꢀ4.44 (d, JRhP = 115.0 Hz), ꢀ143.8 (sep,
JPF = 712 Hz).
Table 1
Crystal data for [(p-cymene)RuCl(PPh3){CH@CPh(PPh3)}](PF6) Æ Et2O
(2a Æ Et2O)a, (6)a,
[Cp*Ir(PMePh2){CH@CPh(PPh3)}](PF6)
and
[Cp*Rh{P(OMe)3}{CH@CPh(PPh3P)}](PF6) Æ H2O (8a Æ H2O)b
Compound
2a Æ Et2O
6
8a Æ H2O
Formula
Molecular
Crystal
C58H60OClP3F6Ru C54H51ClP3F6Ir C39H47O4ClP4F6Rh
2.6. X-ray crystallography – data collection
1116.55
1134.58
956.04
monoclinic
monoclinic
monoclinic
All complexes were recrystallized from CH2Cl2/diethyl
ether. Cell constants of 6 and 8a Æ H2O were determined
from 20 reflections on a Rigaku AFC5S diffractometer.
Data collections were carried out on a Rigaku AFC5S
diffractometer. Intensities were measured by the 2h ꢀ x
system
Space group P21/n (No. 14)
P21/n (No. 14) C2/c (No. 15)
˚
a (A)
18.939(3)
10.391(1)
26.5088(6)
92.9336(5)
5210.2(10)
4
16.287(2)
13.876(3)
24.1512(7)
99.6037(7)
5381(1)
4
42.480(5)
9.069(7)
23.363(5)
107.95(1)
8562(6)
8
˚
b (A)
˚
c (A)
b (°)
˚
scan method using Mo Ka radiation (k = 0.71069 A) at
˚
V (A)
27°. 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. Crystals of 2a Æ Et2O were mounted
at the top of quartz fiber using perfluoro(polyoxopropyl-
ene ethylether), which was set on a MSC/ADSC Quan-
tum CCD/Rigaku AFC8 (ultraX 18) diffractometer.
The measurement was made by using Mo Ka radiation
Z
Dcalc (g cmꢀ3
l (Mo Ka)
)
1.423
1.400
1.483
5.06
26.80
6.74
(cmꢀ1
)
Number of
reflections
2h (°)
11931
12284
55.0
7745
50.0
55.0
Number of
data used
Number of
variables
8759 (I > 3r(I))
6394 (I > 2r(I)) 2377 (I > 2r(I))
631
586
274
˚
c
(k = 0.71069 A) at 0 °C under a cold nitrogen stream.
R: Rw
0.044; 0.049
0.122; 0.125
5.74
0.106; 0.118
2.04
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 the all reflections
measured in the range 2.8° < 2h < 55°. The intensity
images were measured at 0.5° intervals of x for a dura-
tion of 20 s. The frame data were integrated using a
d*TREK program package and the data sets were cor-
rected for absorption using a REQAB program. The
crystal parameters along with data collections are sum-
marized in Table 1.
Goodness-of- 2.21
fitd
a
Measured by Quantum CCD/Rigaku AFC8 diffractometer.
Measured by Rigaku AFC 5S diffractometer.
b
c
P
P
P
R = iFo| ꢀ |Fci/ |Fo| and Rw = [ w(|Fo| ꢀ |Fc|)2/w|Fo|2]1/2 (w = 1/
r2(Fo)).
P
d
GOF = [ w(|Fo| ꢀ |Fc|)2/(No ꢀ Np)]1/2
.
3. Results and discussion
3.1. Alkenyl-phosphonio complexes
Intensities were collected for Lorenz and polarization
effects. Atomic scattering factors were taken from the usual
tabulation of Cromer and Waber [10]. Anomalous disper-
sion effects were included in Fcalc [11]; the values of Df0
and Df00 were those of Creagh and McAuley [12]. All calcu-
lations were performed using the TEXSAN crystallographic
software package [13].
On the treatment of ruthenium complex [(p-cym-
ene)RuCl2(PPh3)] (1) with HC„CR (R = Ph, p-tolyl) and
PPh3 in the presence of KPF6, yellow alkenyl-phophonio
complex
[(g6-p-cymene)RuCl(PPh3){CH@CR(PPh3)}]-
(PF6) (2a: R = Ph; 2b: R = p-tolyl) was obtained in
43.9% (2a) and 40.4% (2b) yields, respectively (Scheme 1).
Similar reactions also occurred in rhodium and iridium
complexes [Cp*MCl2(PPh3)] (3a: M = Rh; 4a: M = Ir), giv-
ing the corresponding alkenyl-phosphonio complexes
[Cp*MCl(PPh3){CH@CPh(PPh3)}](PF6) (5: M = Rh; 6:
M = Ir) as yellow solids in 81.5% (5) and 35.1% (6), respec-
tively (Scheme 2). These complexes were characterized by
2.7. Determination of the structure
The structures of 2a Æ Et2O, 6, and 8a Æ H2O were
solved by Patterson methods (DIRDIF92 PATTY) and
refined on F values for other complexes except on F2 val-
ues for 6. The positions of all non-hydrogen atoms except
8a Æ H2O were refined with anisotropic thermal parameters
by using full-matrix least-squares methods. Occupancies
of the P(2) and P(3) atoms for 8a Æ H2O are 0.5, and the
positions of non-hydrogen atoms except Rh, Cl, four P,
three F and three O atoms refined anisotropically, were
refined with isotropic thermal parameters by using full-
matrix least-squares methods. All hydrogen atoms were
calculated at the ideal positions with the C–H distance
1
the H, 31P{1H} NMR spectra and the elementary analy-
ses. Finally the structures were confirmed by X-ray analy-
ses of 2a and 6.
The 1H NMR spectra of these alkenyl-phosphonio com-
plexes showed two characteristic features: (i) the typical
downfield resonance of the vinylic hydrogen (d 9.63 (2a),
9.61 (2b), 9.69 (5) and 10.36 (6) ppm), in which appeared
as a double doublet for 2a, 2b, and 6, due to the coupling
with the phosphonium, coordinated phosphorus nuclei and
˚
of 0.95 A.

3300
K. Ogata et al. / Inorganica Chimica Acta 360 (2007) 3296–3303
3.3. Reactions of Cp*RhCl2L1 with phenylacetylene and
methyldiphenylphosphine or trimethylphosphite
+
HC CR
PPh3, KPF6
-
PF6
Ru
R
Ph3P
Cl
Ru
C
H
C
Cl
Ph3P
Cl
In order to prepare other alkenyl-phosphonio com-
plexes, the reactions of rhodium complex with phenylacet-
ylene and another phosphine or phosphite were carried out
in the presence of KPF6. Reactions of [Cp*RhCl2(PPh3)]
(3a) with an excess of PMePh2 or P(OMe)3 generated
[Cp*RhClL2](PF6) (7bb: L = PPh2Me; 7cc: L = P(OMe)3)
without forming corresponding alkenyl-phosphonio com-
plexes. the reaction of Cp*RhCl2(P(OMe3)) (3c) with
PPh3
2a (R = Ph)
2b (R = -tolyl)
1
p
Scheme 1. Reaction of (p-cymene)RuCl2(PPh3) with 1-alkynes and PPh3
in the presence of KPF6.
HC CPh
PPh3, KPF6
+
[Cp*RhCl(P(OMe)3)(PPh3)](PF6)
(7ca)
-
PPh3
gave
PF6
M
M
(Scheme 4).
Ph3P
Ph
Cl
Ph3P
Cl
C
C
Cl
PPh3
H
3.4. Reactions of alkenyl-phosphonio complexes
3a (M = Rh)
4a (M = Ir)
5 (M = Rh)
6 (M = Ir)
In regard with the formation of alkenyl-phosphonio
complexes, the synthetic method was limited, but coordi-
nated triphenylphosphine of 5 was readily substituted with
other Lewis bases (L) such as trimethylphosphite or 2,6-
xylyl isocyanide (CNXyl), giving [Cp*RhClL{CH@CPh-
(PPh3)}](PF6) (8a: L = P(OMe)3; 8b: CNXyl) (Scheme 5).
Scheme 2. Reactions of Cp*MCl2(PPh3) (M = Rh, Ir) with phenylacety-
lene and PPh3 in the presence of KPF6.
as two double doublets for 5 due to the coupling with two
phosphine and rhodium nuclei and (ii) in ruthenium com-
plexes 2a and 2b, two resonances (d 0.91 (d) and 1.02(d))
for methyl protons of isopropyl group, as a result of
inequivalence arising from the chiral center of the Ru
atom.
1
The H NMR spectrum of 8a showed two doublets at d
1.44 and 3.73 due to Cp* and methoxy protons, respec-
tively. The vinylic proton appeared at d 9.80 as a two dou-
ble doublets (J = 33.1, 4.8, 4.4 Hz) due to the coupling with
two P and rhodium nucleus. In the 31P{1H} NMR spec-
trum, two double doublets appeared at d 124.0 and 19.4
due to the coupling with two P atoms, respectively.
The 31P{1H} NMR spectra of ruthenium complexes (2a
and 2b) and iridium complex (6) showed two singlets at d
25.8 and 18.9 for 2a, at d 37.4 and 18.6 for 2b, and at d
25.8 and 4.09 for 6. In case of rhodium complex 5, two
doublets were observed at d 36.8 (d) and 21.5 (d) by cou-
pling with a rhodium nucleus. The former is assigned to
a coordinated phosphine ligand and the latter to a phos-
phonium P nucleus, in comparison with those of the parent
complexes.
The IR spectrum of 8b showed a characteristic band at
1
2162 cmꢀ1 for a terminal isocyanide. The H NMR spec-
trum showed two singlets at d 1.63 and 2.15 due to Cp*
and methyl protons of xylyl isocyanide ligand, respectively.
The vinylic proton appeared at d 9.15 as a double doublet
due to the coupling with phosphonium P and rhodium
nucleus. The 31P{1H} NMR spectrum of 8b showed a dou-
blet at 19.2 ppm.
3.2. Reaction pathway
3.5. Reactions of binuclear complexes with phenylacetylene
and triphenylphosphine
An initial reaction consists of p-alkyne intermediate,
accompanying by a nucleophilic attack of phosphine on
the carbon of the coordinated alkyne as depicted in the
reaction of indenyl–ruthenium complexes (Scheme 3) [4].
The formations of vinylidene species in the reactions of
ruthenium, rhodium and iridium complex with 1-alkyne
were supported as previously reported our papers [2]. The
results show the existence of an vinylidene–alkyne equilib-
rium in these complexes.
Similar reactions were carried out for diphosphine com-
plexes (Scheme 6). Reaction of [(Cp*RhCl2)2(dppp)]-
(dppp = Ph2P(CH2)3PPh2) (9a) with phenylacetylene and
PPh3 in the presence of KPF6 generated [{Cp*RhCl-
(PPh3)}2(dppp)](PF6)2 (10), whereas that of [(Cp*RhCl2)2
-(dppm)] (dppm = Ph2PCH2PPh2) (9b) generated 5a and
a chelate complex [Cp*RhCl(g2-dppm)](PF6) (11). The
+
HC CPh
PPh3, KPF6
+
-
PF6
-
PPh3
PF6
Ph
Rh
Rh
Cl
Rh
Cl
Ph
Ph3P
C
Ph3P
Ph3P
Cl
Cl
3a
C
C
C
H
PPh3
H
5
Scheme 3. Possible pathway for the formation of the alkenyl-phosphonio complexes.

K. Ogata et al. / Inorganica Chimica Acta 360 (2007) 3296–3303
3301
and 8a contained diethylether or H2O as solvate molecule,
respectively. The molecules have the piano–stool struc-
tures. The metal atom bonded to triphenylphosphine, a
HC CPh
L2, KPF6
+
-
Rh
PF6
L1
Cl
Rh
Ph
L2
L1
Cl
Cl
3a (L1 = PPh3)
3c (L1 = P(OMe)3)
C
C
H
5
+
-
L2 = PPh3
PF6
Rh
Ph3P
(MeO)3P
Cl
7ca (from 3c)
+
L2 = PMePh2
P(OMe)3
-
PF6
Rh
Cl
L2
L2
7bb (L2 = PMePh2 (from 3a)
7cc (L2 = P(OMe)3 (from 3a)
Scheme 4. Reaction of Cp*RhCl2L1 (L1 = PPh3, P(OMe)3) with phenyl-
acetylene and L2 (L2 = PPh3, PMePh2, P(OMe)3) in the presence of KPF6.
Fig. 1. ORTEP drawings for the complex cation of 2a; the PF6 anion and
Et2O were omitted for clarity and thermal ellipsoids are drawn to
encompass 50% probability.
+
+
-
-
PF6
L
PF6
Rh
Rh
Ph
Ph
L
Ph3P
Cl
C
H
C
C
H
C
Cl
PPh3
PPh3
8a (L = P(OMe)3)
8b (L = CNXyl)
5
Scheme 5. Reaction of [Cp*RhCl(PPh3){CH@CPh(PPh3)}](PF6) with
P(OMe)3 or CNXyl.
reaction likely arose from the strong chelating ability of
dppm ligand. The reaction consists of an occurrence of
an intermediate ‘‘Cp*RhCl2’’ (or [Cp*RhCl2]2) by chelating
of the dppm ligand to give 11, accompanying by addition
of PPh3 to the intermediate to afford Cp*RhCl2(PPh3) that
resulted in the formation of 5a.
3.6. Crystal structures
Perspective drawings of 2a, 6 and 8a with the atomic
numbering scheme are given in Figs. 1–3 and selected bond
lengths and angles are listed in Tables 2–4. Complexes 2a
Fig. 2. ORTEP drawings for the complex cation of 6; the PF6 anion was
omitted for clarity and thermal ellipsoids are drawn to encompass 50%
probability.
2+
-
2PF6
n = 3
Rh
Rh
Ph3P
PPh3
P
(CH2)3
P
Ph2
Ph2
Cl
Cl
HC CPh
10
PPh3, KPF6
Rh
Rh
Cl
Cl
P
(CH2)n
P
+
+
Ph2
Ph2
Cl
Cl
-
-
PF6
PF6
n = 1
9a (n = 3)
9b (n = 1)
Rh
Ph
Rh
Ph3P
Cl
+
Cl
C
H
Ph2P
C
PPh3
PPh2
5a
11
Scheme 6. Reaction of Cp*RhCl2(diphosphine) with phenylacetylene and PPh3 in the presence of KPF6.

3302
K. Ogata et al. / Inorganica Chimica Acta 360 (2007) 3296–3303
[(C9H7)Ru{CH@C(PPh3)R}(PPh3)2](BF4) (R = CH@CH-
˚
(C5H4)Fe(C5H5)) (2.039(8) A) [4], R = 1-cyclohexenyl
˚
˚
(2.045(6) A [3]). The C1–C2 bond length of 1.343(4) A is
the usual C@C bond length. The P–Cb bond length in each
complex is not different from those found in other P–C
ones, indicating to be a phosphonium type. Accuracy for
the data of 6 and 8a is too low to discuss in detail.
4. Conclusion
This paper provides a convenient and selective synthesis
of alkenyl-phosphonio derivatives from ruthenium, rho-
dium and iridium complexes, 1-alkyne and triphenylphos-
phine in the presence of KPF6. The coordinated
triphenylphosphine of alkenyl-phosphnio complex was
readily substituted with other Lewis bases such as trim-
ethylphosphite or xylyl isocyanide, giving trimethylphosph-
ite or xylyl isocyanide complexes. These methods may be
used for the synthesis of various alkenyl-phosphonio
complexes.
Fig. 3. ORTEP drawings for the complex cation of 8a; the PF6 anion and
H2O were omitted for clarity and thermal ellipsoids are drawn to
encompass 50% probability.
Cl atom and an alkenyl-phosphonio group, in which the
phosphine bonds to the Cb atom of the alkenyl group with
an E configuration.
Acknowledgements
˚
The Ru–C(1) bond length of 2a is 2.053(3) A, slightly
The authors thank Professor Shigetoshi Takahashi and
Dr Fumie Takei of The Institute of Scientific and Industrial
Research, Osaka University for performing the FAB mass
spectrometry measurements. This work was partially supported
longer than those reported for other alkenyl-phosphonio-
ruthenium(II) complexes, i.e., [(1,2,3-Me3C9H4)Ru{CH-
˚
@C(PPh3)Ph}(CO)(PPh3)](BF4) (2.039(7) A) [4] and
Table 2
Selected bond lengths and angles for [(p-cymene)RuCl(PPh3){CH@CPh(PPh3)}](PF6) Æ Et2O (2a Æ Et2O)
Ru(1)–P(2)
C(1)–C(2)
P(1)–C(15)
P(2)–C(33)
2.3495(8)
1.343(4)
1.809(3)
1.830(3)
Ru(1)–Cl(1)
P(1)–C(2)
P(1)–C(21)
P(2)–C(39)
2.4234(7)
1.801(2)
1.809(3)
1.840(3)
Ru(1)–C(1)
P(1)–C(9)
P(2)–C(27)
2.053(3)
1.798(3)
1.846(3)
Cl(1)–Ru(1)–P(2)
Ru(1)–C(1)–C(2)
P(1)–C(2)–C(3)
89.73(3)
131.3(2)
115.5(2)
Cl(1)–Ru(1)–C(1)
C(1)–C(2)–P(1)
87.00(8)
115.9(2)
P(2)–Ru(1)–C(1)
C(1)–C(2)–C(3)
87.13(8)
128.5(3)
Table 3
Selected bond lengths and angles for [Cp*IrClPPh3{CH@CPh(PPh3)}](PF6) (6)
Ir–P(2)
2.311(6)
1.42(3)
1.81(2)
1.80(2)
Ir–Cl
2.406(5)
1.80(2)
1.81(2)
1.82(3)
Ir–C(1)
P(1)–C(9)
P(2)–C(27)
1.99(2)
1.80(2)
1.81(2)
C(1)–C(2)
P(1)–C(15)
P(2)–C(33)
P(1)–C(2)
P(1)–C(21)
P(2)–C(39)
Cl–Ir–P(2)
Ir(1)–C(1)–C(2)
P(1)–C(2)–C(3)
89.3(2)
133(1)
115(1)
Cl–Ir–C(1)
C(1)–C(2)–P(1)
89.7(5)
115(1)
P(2)–Ir–C(1)
C(1)–C(2)–C(3)
86.7(5)
129(1)
Table 4
Selected bond lengths and angles for [Cp*RhCl{P(OMe)3}{CH@CPh(PPh3)}](PF6) Æ H2O (8a Æ H2O)
Rh(1)–Cl(1)
P(1)–C(12)
P(1)–C(25)
P–O(2)
2.410(7)
1.84(2)
1.80(3)
1.55(2)
Rh(1)–P
2.227(8)
1.36(3)
1.79(3)
1.57(2)
Rh(1)–C(11)
P(1)–C(19)
P–O(1)
1.99(2)
1.84(3)
1.59(2)
C(11)–C(12)
P(1)–C(31)
P–O(3)
Cl(1)–Rh(1)–P
Rh(1)–C(11)–C(12)
C(13)–C(12)–P(1)
89.3(3)
137(1)
115(1)
Cl(1)–Rh(1)–C(11)
C(11)–C(12)–P(1)
85.7(7)
116(1)
P–Rh(1)–C(11)
C(11)–C(12)–C(13)
92.8(7)
127(2)

K. Ogata et al. / Inorganica Chimica Acta 360 (2007) 3296–3303
3303
(b) K. Ogata, J. Seta, K. Sugawara, N. Tsutsumi, Y. Yamamoto, K.
Kuge, K. Tatsumi, Inorg. Chim. Acta. 359 (2006) 1549.
[3] V. Cadierno, M.P. Gamasa, J. Gimeno, J. Borge, S.G. Granda,
Organometallics 16 (1997) 3178.
[4] V. Cadierno, M.P. Gamasa, J. Gimeno, C.G. Bernardo, E.P.
Carreno, S.G. Granda, Organometallics 20 (2001) 5177.
[5] (a) C.S. Chin, Y. Park, J. Kim, H. Lee, J. Chem. Soc., Chem.
Commun. (1995) 1495;
by a Grant-in Aid for Scientific Research from the Ministry
of Education, Science, Culture and Sports, Japan.
Appendix A. Supplementary material
CCDC 163784, 177720 and 629537 contain the supple-
mentary crystallographic data for 2a, 6 and 8a. These data
can be obtained free of charge via http://www.ccdc.cam.
ac.uk/conts/retrieving.html, or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk. Supplementary data associated
with this article can be found, in the online version, at
doi:10.1016/j.ica.2007.03.053.
(b) C.S. Chin, H. Lee, M. Oh, Organometallics 16 (1999) 4810;
(c) C.S. Chin, H. Cho, G. Won, M. Oh, K.M. Ok, Organometallics 18
(1999) 4810;
(d) C.S. Chin, M. Lee, M. Oh, G. Won, M. Kim, Y.J. Park,
Organometallics 19 (2000) 1572;
(e) C.S. Chin, M. Kin, H. Lee, Organometallics 21 (2002) 1679;
(f) C.S. Chin, M. Kim, G. Won, H. Jung, H. Lee, J. Chem. Soc.,
Dalton Trans. (2003) 2325;
(g) C.S. Chin, Y. Kim, H. Lee, Inorg. Chim. Acta 357 (2004) 3064.
[6] Y. Yamamoto, K. Ogata, K. Kuge, K. Tatsumi, Inorg. Chem.
Commun. 5 (2002) 862.
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