Reactions of (η6-C6Me6)RuCl(MDMPP-P,O) and (η6-C6Me6)RuCl(BDMPP-P,O,O) complexes with Lewis bases or alkynes, where MDMPP-P,O=P(2-O-6-MeOC6H3)Ph2 and BDMPP-P,O,O=P(2-O-6-MeOC6H3)2{2,6-(MeO) 2C6H3}

Article abstract of DOI:10.1016/S0022-328X(98)00771-2

Reaction of [(η⁶-C₆Me₆)RuCl(MDMPP-P,O)] 1 (MDMPP-P,O=P(2-O-6-MeOC₆H₃)Ph₂] with CO under high pressure at 95° gave RuCl(CO)₃(MDMPP-P,O) 2. [(η⁶-p-cymene)Ru(TDMPP-P,O,O)] (TDMPP-P,O,O=P(2-O-6-MeOC₆H₃)₂{2,6-(MeO) ₂C₆H₃}) reacted with CO or CO/2,6-xylyl isocyanide under high pressure to form Ru(CO)₃(TDMPP-P,O,O) 4 or Ru(CO)₂(XyINC)(TDMPP-P,O,O) 5 (Xyl=2,6-Me₂C₆H₃), respectively. Reactions of 1 with Lewis bases in the presence of NH₄PF₆ gave [(η⁶-C₆Me₆)RuL(MDMPP-P,O)](PF₆) 6 (L=CO, XylNC). Complex 1 reacted with mono-substituted acetylenes in acetone in the presence of bases to form the metal alkynyl complexes [(η⁶-C₆Me₆)Ru(CCR)(MDMPP-P,O)] 7. Similar reaction of 1 with PhCCH in the presence of NaPF₆ in acetone or MeOH gave a vinylidene 8a (R=C=CHPh) and a carbene complex 9a (R=CCH₂Ph(OMe)) [(η⁶-C₆Me₆)Ru(=R)(MDMPP-P,O)](PF ₆), respectively. A reaction of 1 with HCCCMe₂OH and NaPF₆ in MeOH gave a metallabutadiene complex 10c [(η⁶-C₆Me₆) Ru{=C(OMe)CH=CMe₂}(MDMPP-P,O)]. X-ray analyses of 6b (L=XylNC), 7a (R=Ph) and 7e (R=CH₂OH) were carried out to confirm the structures; 6b, monoclinic, space group P2₁/c (No. 14), a=9.910(8) A, b=25.370(7) A, c=16.020(7) A, β=105.29(5)°,V=3885(7) A³, Z=4, R=0.050, R_w=0.053 for 4064 reflections (I 3.0σ(I)); 7a, orthorhombic, space group Pbca, a=17.222(4) A, b=23.772(8) A, c=16.003(8) A, V=6552(7) A³, Z=8, R=0.052, R_w=0.052 for 1836 reflections (I 3.0σ(I)); 7e, triclinic, space group P₁ (No. 2), a=10.639(4) A, b=14.778(3) A, c=10.214(3) A, α=97.05(2)°, β=113.01(2)°, γ=79.12(2)°, V=1449(2) A³, Z=2, R=0.041, R_w=0.040 for 3270 reflections (I 3.0σ(I)).

Full text of DOI:10.1016/S0022-328X(98)00771-2

Journal of Organometallic Chemistry 569 (1998) 29–37
Reactions of (p6-C6Me6)RuCl(MDMPP-P,O) and
(p6-C6Me6)RuCl(BDMPP-P,O,O) complexes with Lewis bases or
alkynes, where MDMPP-P,OꢀP(2-O-6-MeOC6H3)Ph2 and
BDMPP-P,O,OꢀP(2-O-6-MeOC6H3)2{2,6-(MeO)2C6H3}1
Yasuhiro Yamamoto a,*, Tomoaki Tanase b, Chihiro Sudoh a, Tatsuhiro Turuta a
a Department of Chemistry, Faculty of Science, Toho Uni6ersity, Miyama, Funabashi, Chiba 274, Japan
b Department of Chemistry, Nara Women’s Uni6ersity, Nara, Japan
Received 20 February 1998
Abstract
Reaction of [(p6-C6Me6)RuCl(MDMPP-P,O)] 1 (MDMPP-P,OꢀP(2-O-6-MeOC6H3)Ph2] with CO under high pressure at 95°
gave RuCl(CO)3(MDMPP-P,O) 2. [(p6-p-cymene)Ru(TDMPP-P,O,O)] (TDMPP-P,O,OꢀP(2-O-6-MeOC6H3)2{2,6-(MeO)2C6H3})
reacted with CO or CO/2,6-xylyl isocyanide under high pressure to form Ru(CO)3(TDMPP-P,O,O)
4
or
Ru(CO)2(XyINC)(TDMPP-P,O,O) 5 (Xyl=2,6-Me2C6H3), respectively. Reactions of 1 with Lewis bases in the presence of
NH4PF6 gave [(p6-C6Me6)RuL(MDMPP-P,O)](PF6) 6 (L=CO, XylNC). Complex 1 reacted with mono-substituted acetylenes in
acetone in the presence of bases to form the metal alkynyl complexes [(p6-C6Me6)Ru(CꢁCR)(MDMPP-P,O)] 7. Similar reaction
of 1 with PhCꢁCH in the presence of NaPF6 in acetone or MeOH gave a vinylidene 8a (R=CꢀCHPh) and a carbene complex
9a (R=CCH2Ph(OMe)) [(p6-C6Me6)Ru(ꢀR)(MDMPP-P,O)](PF6), respectively. A reaction of 1 with HCꢁCCMe2OH and NaPF6
in MeOH gave a metallabutadiene complex 10c [(p6-C6Me6) Ru{ꢀC(OMe)CHꢀCMe2}(MDMPP-P,O)]. X-ray analyses of 6b
(L=XylNC), 7a (R=Ph) and 7e (R=CH2OH) were carried out to confirm the structures; 6b, monoclinic, space group P21/c
3
˚
˚
˚
˚
(No. 14), a=9.910(8) A, b=25.370(7) A, c=16.020(7) A, i=105.29(5)°,V=3885(7) A , Z=4, R=0.050, Rw=0.053 for 4064
3
˚
˚
˚
˚
reflections (I\3.0|(I)); 7a, orthorhombic, space group Pbca, a=17.222(4) A, b=23.772(8) A, c=16.003(8) A, V=6552(7) A ,
Z=8, R=0.052, Rw=0.052 for 1836 reflections (I\3.0|(I)); 7e, triclinic, space group P1 (No. 2), a=10.639(4) A, b=14.778(3)
A, c=10.214(3) A, h=97.05(2)°, i=113.01(2)°, k=79.12(2)°, V=1449(2) A , Z=2, R=0.041, Rw=0.040 for 3270 reflections
˚
3
˚
˚
˚
(I\3.0|(I)). © 1998 Elsevier Science S.A. All rights reserved.
Keywords: Bis[dichloro(p6-arene)ruthenium(II)]; (2,6-Dimethoxyphenyl)diphenylphosphine; Ruthenium alkyne complexes
1. Introduction
These phosphines are functionalized phosphines which
have the potential to form hemilable chelates in a
similar manner to phosphinoethers [3]. We have shown
previously that complexes with various coordination
modes such as P, (P,O), or (P,O,O%) chelation were
Tertiary aromatic phosphines bearing methoxy
groups
at
2-
and
6-positions
such
as
P[2,6(MeO)2C6H3]3, P[2,4,6-(MeO)3C6H2]3, and their re-
lated phosphines have provided characteristic reactivity
because of the high basicity and steric bulkiness [1,2].
obtained
in
the
coordination
chemistry
of
P[2,6(MeO)2C6H3]3 (TDMPP), PPh[2,6-(MeO)2C6H3]2
(BDMPP), and PPh2[2,6-(MeO)2C6H3] (MDMPP) with
bis[dichloro(p6-arene)ruthenium(II)], depending on are-
nes and phosphines [4]. Reaction of MDMPP with
bis[dichloro(p6-arene)ruthenium] led to an elimination
* Corresponding author. Fax: +81 974 751855.
1 Dedicated to Professor Akira Nakamura on the occassion of his
retirement from Osaka University.
0022-328X/98/$ - see front matter © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00771-2

30
Y. Yamamoto et al. / Journal of Organometallic Chemistry 569 (1998) 29–37
Cl2. IR(Nujol): 2042, 1956, 1932 (CꢁO) cm−1. UV-vis
(CH2Cl2): umax 301(4.06), 262(sh) nm. Anal. Calc. for
C25.5H22O9ClPRu: C, 47.86; H, 3.47. Found: C, 48.33;
H, 3.70.
of MeCl to give [(p6-arene)RuCl(MDMPP-P,O)] 1
(MDMPP-P,OꢀP(2-O-6-MeOC6H3)Ph2] bearing the
P,O chelation as a bidentate ligand, whereas the reac-
tion with TDMPP eliminated two molecules of MeCl to
yield (p6-arene)Ru(TDMPP-P,O,O%)
3
(TDMPP-
P,O,O%ꢀ[P(2-O-6-MeOC6H3)2{2,6-(MeO)2 C6H3}] bear-
ing the P,O,O% chelation as a tridentate ligand. In some
attempts to examine the stability of the P,O-chelation
and their reactivities to various small molecules, we
carried out the reactions of these complexes 1 and 3
with Lewis base and acetylenes.
2.1.3. Reaction of 3 with CO and xylyl isocyanide
A mixture of 3 (57 mg, 0.078 mmol), xylyl isocyanide
(39 mg, 0.298 mmol) and 45 kg cm−2 of CO in CH3CN
(3 ml) and toluene (4 ml) in a 100 ml-stainless steel
autoclave was heated at 95°C for 3.5 h. A solution
color changed from yellow to very pale yellow. The
solvent was removed under reduced pressure, and the
residue was recrystallized from CH2Cl2 and diethyl
ether to give colorless crystals (47.8 mg, 87.4%) of
Ru(TDMPP-P,O,O)(CO)2(XylNC) 5. FAB mass (m/z):
701 (M+), 645 (M–2CO+), 514 (M–2CO–RNC+).
UV-vis (CH2Cl2): u ca. 300 (sh) nm. IR(Nujol): 2176
2. Experimental
All reactions were carried out under nitrogen atmo-
sphere. Arene ruthenium complexes [4], (p6-
C6Me6)RuCl(MDMPP-P,O)
1,
(p6-p-cymene)Ru-
1
(NꢁC), 2031, 1970 (CꢁO), 1582, 1549 cm−1. H-NMR
(TDMPP-P,O,O%) 3, and xylyl isocyanide [5] were pre-
pared according to the literature. MeCN and CH2Cl2
were distilled over CaH2 and other reagents were used
as commercially available. The infrared and electronic
absorption spectra were measured on FT/IR-5300 and
U-best 30 spectrometers, respectively. NMR spec-
troscopy was carried out on a Bruker AC250. 1H-NMR
spectra were measured at 250 MHz using tetramethylsi-
lane as an internal reference and 31P{1H}-NMR spectra
were measured using 85% H3PO4 as an external refer-
ence. The FAB mass spectra were measured on a
JMS-Dx300 spectrometer.
(CDCl3): l 2.60 (s, o-Me), 5.51, 3.57 (s, MeO), 5.9–7.5
(c, Ph) ppm.
2.1.4. Reaction of 1 with CO in the presence of
NH4PF6
Carbon monoxide was bubbled through a solution of
1 (100 mg, 0.16 mmol) in CH2Cl2 (10 ml) at room
temperature, and NH4PF6 (140 mg, 0.83 mmol) in
acetone (5 ml) was added to the solution. The mixture
was stirred for 4 h, in which CO was bubbled each
hour. The solvent was removed under reduced pressure
and the residue was extracted with CH2Cl2, followed by
filtration of the extract through a glass filter (G4).
Removal of the solvent and crystallization of the
residue from CH2Cl2 and diethyl ether gave yellow
crystals of [(p6-C6Me6)Ru(CO)(MDMPP-P,O)](PF6) 6a
(35 mg, 30%). IR(Nujol): 2004 (CꢁO), 1587, 1552, 835
(PF6) cm−1. UV-vis (CH2Cl2): umax 333 (sh), 285 (sh)
2.1. Reactions of complexes 1 and 3
2.1.1. Reaction of 1 with CO
A mixture of 1 (50 mg, 0.08 mmol) and 45 kg cm−2
of CO in CH3CN (3 ml) and toluene (4 ml) was charged
in a 100 ml-stainless steel autoclave and heated at 95°C
for 4.5 h. A solution color changed from yellow to pale
yellow. The solvent was removed under reduced pres-
sure, and the residue was recrystallized from CH2Cl2
and diethyl ether to give pale yellow crystals (25 mg,
59%) of RuCl[P(2-O-6-MeOC6H3)Ph2](CO)3 2. IR(Nu-
jol): 2058, 1986, 1946 (CꢁO) cm−1. Anal. Calc. for
C22H13NO5Cl PRu: C, 50.06; H, 3.06. Found: C, 50.02;
H, 3.37.
1
nm. H-MR(CDCl3): l 2.04 (s, C6Me6), 3.39 (s, MeO),
6.1–7.6 (m, Ph). 31P{1H}-NMR (CDCl3): l 52.0 (s),
−114.7 (sep. PF6, JPF=708 Hz). Anal. Calc. for
C32H34O3F6P2Ru: C, 51.54; H, 4.60. Found: C, 51.49;
H, 4.68.
2.1.5. Reaction of 1 with xylyl isocyanide in the
presence of NH4PF6
To a mixture of 1 (100 mg, 0.16 mmol) and xylyl
isocyanide (44 mg, 0.33 mmol) in CH2Cl2 (10 ml) was
added NH4PF6 (140 mg, 0.83 mmol) in acetone (5 ml).
After the mixture was stirred for 2 h at room tempera-
ture, the solvent was removed under reduced pressure
and the residue was extracted with CH2Cl2, followed by
filtration of the extract through a glass filter (G4).
Removal of the solvent and crystallization of the
residue from CH2Cl2 and diethyl ether gave yellow
crystals of [(p6-C6Me6)Ru(XylNC)(MDMPP-P,O)]
2.1.2. Reaction of 3 with CO
A mixture of 3 (57 mg, 0.078 mmol) and 45 kg cm−2
of CO in CH3CN (3 ml) and toluene (4 ml) in a 100
ml-stainless steel autoclave was heated at 95°C for 4.5
h. A solution color changed from yellow to very pale
yellow. The solvent was removed under reduced pres-
sure, and the residue was recrystallized from CH2Cl2
and diethyl ether to give colorless crystals (23 mg,
46.1%) of Ru(TDMPP-P,O,O)(CO)3 ·12CH2Cl2 4·21CH2-

Y. Yamamoto et al. / Journal of Organometallic Chemistry 569 (1998) 29–37
31
(PF6) (78 mg, 60%). IR(Nujol): 2135 (NꢁC), 1581, 1548,
2.1.7. Reaction of 1 with HCꢁCCOOMe in the
presence of potassium hydroxide
To a solution of 1 (66.8 mg, 0.11 mmol) and
HCꢁCCOOMe (0.18ml, 2.0 mmol) in CH2Cl2
844 (PF6) cm−1. UV-vis (CH2Cl2): 330 (sh), 274 (sh)
nm. 1H-NMR(CDCl3): l 1.84 (s, o-Me), 2.05 (s,
C6Me6), 3.33 (s, MeO), 6.0–7.6 (m, Ph) ppm. 31P{1H}-
NMR (CDCl3): l 53.6 (s), −114.7 (sep. JPF=709 Hz,
PF6) ppm. Anal. Calc. for C40H43NO2F6P2Ru: C,
56.60; H, 5.11; N, 1.65. Found: C, 56.64; H, 5.13; N,
1.85.
/
methanol (10 ml/10 ml) was added 0.38 ml (0.11 mmol)
of a 0.277 mmol methanol solution containing potas-
sium hydroxide at room temperature. After stirring for
15 min, the solvent was removed under reduced pres-
sure and the residue was extracted with CH2Cl2, fol-
lowed by filtration through a glass filter (G4). The
solution was removed to ca. 3 ml and hexane was
added to give orange yellow crystals (p6-
C6Me6)Ru(CꢁCCOOMe)(MDMPP-P,O) · 12CH2Cl2
7b·12CH2Cl2 (37.7 mg, 49%). IR(Nujol): 2081 (CꢁC),
2.1.6. Reaction of 1 with PhCꢁCH in the presence of
potassium hydroxide
To a solution of 1 (66.8 mg, 0.11 mmol) and phenyl
acetylene (0.37 ml, 3.4 mmol) in CH2Cl2/methanol (10
ml/10 ml) was added 0.55 ml (0.152 mmol) of a 0.277
mmol methanol solution containing potassium hydrox-
ide at room temperature. After stirring for 24 h, the
solvent was removed under reduced pressure and the
residue was extracted with CH2Cl2, followed by filtra-
tion through a glass filter (G4). The filtrate was chro-
matographed on alumina, using CH2Cl2 as an eluant.
Removal of the yellow eluate and crystallization of the
residue from ether and hexane gave orange yellow
crystals (p6-C6Me6)Ru(CꢁCPh)(MDMPP-P,O)·21H2O
7a·12H2O (75.7 mg, 65%). IR(Nujol): 2089 (CꢁC), 1580,
1669 (CꢀO), 1580, 1543 cm−1 1H-NMR(CDCl3): l
.
1.88 (s, C6Me6), 3.27, 3.30 (s, MeO, COOMe), 5.27 (s,
CH2Cl2), 5.84–7.8 (m, Ph) ppm. 31P{1H}-NMR
(CDCl3):
l
58.1 (s) ppm. Anal. Calc. for
C35.5H38O4CIPRu: C, 61.25; H, 5.50. Found: C, 61.09;
H, 5.21.
2.1.8. Reaction of 1 with HCꢁCCH2OH in the
presence of potassium hydroxide
To a solution of 1 (66.8 mg, 0.11 mmol) and 2-
propyne-1-ol (0.22 ml, 3.78 mmol) in CH2Cl2 /methanol
(10 ml/10 ml) was added 0.38 ml (0.11 mmol) of a 0.277
mmol methanol solution containing potassium hydrox-
ide at room temperature. After stirring for 15 min, the
solvent was removed under reduced pressure and the
1
1543 cm−1. H-NMR(CDCl3): l 1.91 (s, C6Me6), 3.03
(s, MeO), 5.84–7.8 (m, Ph) ppm. 31P{1H}-NMR
(CDCl3):
l
58.1 (s) ppm. Anal. Calc. for
C39H40O2.5PRu: C, 68.81; H, 5.92. Found: C, 68.59; H,
5.54.
Table 1
Crystal data of [(p6-C6Me6)Ru(XylNC)[P(2-O-6-MeOC6H3)Ph2][PF6] 6b, (p6-C6Me6)Ru(CꢁCPh)[P(2-O-6-MeOC6H3)Ph2] 7a and (p6-
C6Me6)Ru(CꢁCCH2OH)[P(2-O-6-MeOC6H3)Ph2] 7e.
Compound
6b
7a
7e
Formula
Molecular weight
Color
C
846.79
Yellow
0.50×0.50×0.50
Monoclinic
P21/c (no. l4)
40H43NO2F6P2Ru
C39H39O2PRu
671.78
Orange yellow
0.50×0.50×0.38
Orthorhombic
Pbca (no.)
C34H37O3PRu
625.71
Yellow
0.35×0.22×0.08
Triclinic
P1 (no. 2)
Crystal dimension (mm)
Crystal system
Space group
Lattice parameters
a
9.910(8)
25.370(7)
16.020(7)
90.0
105.29(5)
90.0
3885(7)
4
1.447
17.222(4)
23.772(8)
16.003(8)
90.0
90.0
90.0
6552(7)
8
1.362
5.48
10.639(4)
14.778(3)
10.214(3)
97.05(2)
113.01(2)
79.12(2)
1449(2)
2
˚
b (A)
˚
c (A)
h (°)
i (°)
k (°)
3
˚
V (A )
Z
Dcalc. (g cm−3
v cm−1
F(000)
)
1.434
6.16
648
5.38
1736
2784
No. of data (I\3.0|(I))
No. of variables
R; Raw
4064
469
0.050; 0.053
1.86
1836
388
0.052; 0.052
1.34
3270
353
0.041; 0.040
1.32
GOF
2 1/2
a R=ꢀꢁꢁFoꢁ−ꢁFcꢁꢁ/ꢀꢁFoꢁ and Rw=[ꢀw(ꢁFoꢁ−ꢁFcꢁ)2/ꢀwꢁFoꢁ ]
.
GOF, [ꢀw(ꢁFoꢁ−ꢁFcꢁ)2/ꢀ(No−Nv]1/2 where No is the number of data; Nv is the number of variables.

32
Y. Yamamoto et al. / Journal of Organometallic Chemistry 569 (1998) 29–37
Scheme 1.
residue was extracted with CH2Cl2, followed by filtra-
tion through a glass filter (G4). The solvent was re-
moved under reduced pressure and the residue was
recrystallized from ether/hexane to give yellow crystals
of (p6-C6Me6)Ru(CꢁCCH2OH)(MDMPP-P,O)]·21H2O
7e·12H2O (49.2 mg, 71%). IR(Nujol): 2116 (CꢁC), 1580,
7d·14H2O (37.4 mg, 53%). IR(Nujol): 2093 (CꢁC), 1580,
1545 cm−1. 1H-NMR(CDCl3): l 0.81*, 1.40 (dd, JPH
6.3 Hz), 1.86, 1.87* (s, C6Me6), 2.03 (br, OH,), 3.26,
3.27* (s, MeO), 3.98 (m, CH), 5.9–7.8 (m, Ph) ppm.
31P{1H}-NMR (CDCl3): l 58.1, 58.4* (s) ppm (isomers
A* and B). Anal. Calc. for C35H39.5O3.25PRu: C, 65.25;
H, 6.18. Found: C, 65.53; H, 5.60.
=
1
1543 cm−1. H-NMR(CDCl3): l 1.87 (s, C6Me6), 2.04
(br, OH, 1H), 3.27 (s, MeO), 3.65–3.81 (m, CH2),
5.9–7.7 (m, Ph) ppm. 31P{1H}-NMR (CDCl3): l 57.9
(s) ppm. Anal. Calc. for C34H38O3.5PRu: C, 63.44; H,
6.11. Found: C, 63.51; H, 5.73.
According to the procedure similar to that described
above, yellow complex (p6-C6Me6)Ru(CꢁCCMe2OH)
(MDMPP-P,O)·14CH2Cl2 7e·41CH2Cl2 (39.1 mg, 53%)
was obtained from the reaction of 1 (66.8 mg, 0.11
mmol) with HCꢁCCMe2OH (0.20 ml, 2.06 mmol). IR(-
2.1.9. Reaction of 1 with HCꢁCCH(Me)OH in the
presence of potassium hydroxide
Nujol): 2098 (CꢁC), 1582, 1541 cm−1 1H-NMR
.
(CDCl3): l 1.00, 1.01 (s, Me), 1.87 (s, C6Me6), 2.04 (br,
OH), 3.27 (s, MeO), 5.9–7.4 (m, Ph) ppm. 31P{1H}-
NMR (CDCl3): 558.1 (s) ppm. Anal. Calc. for
To a solution of 1 (66.8 mg, 0.11 mmol) and 1-bu-
tyne-3-ol (0.27 ml, 3.66 mmol) in CH2Cl2 /methanol (10
ml/10 ml) was added 0.38 ml (0.11 mmol) of a 0.277
mmol methanol solution containing potassium hydrox-
ide at room temperature. After stirring for 30 min, the
solvent was removed under reduced pressure and the
residue was extracted with CH2Cl2, followed by filtra-
tion through a glass filter (G4). The solvent was re-
moved under reduced pressure and the residue was
washed with hexane to give yellow crystals of (p6-
C6Me6)Ru(CꢁCCH(Me)OH)(MDMPP-P,O)·14H2O
C
36.25H41.5O3Cl0.5PRu: C, 65.25; H, 6.18. Found: C,
65.53; H, 5.60.
2.1.10. Reaction of 1 with PhCꢁCH in the presence of
NaPF6 in CH2Cl2/acetone
To a mixture of 1 (66.8 mg, 0.11 mmol) and
PhCꢁCH (0.25 ml) in CH2Cl2 (5 ml) and acetone (5 ml)
was added NaPF6 (25 mg, 0.15 mmol) at room temper-
ature. After 15 h, the solvent was removed at reduced

Y. Yamamoto et al. / Journal of Organometallic Chemistry 569 (1998) 29–37
33
Scheme 2.
J
PF=708 Hz, PF6) ppm. Anal. Calc. for
pressure and the residue was recrystallized from CH2Cl2
and Et2O to give 8a·14CH2Cl2 (56.5 mg, 76.2%) as
orange crystals. IR(Nujol): 1620 (CꢀC), 841 (PF6) cm−
C37H44O3P2F6Ru: C, 53.55; H, 5.34. Found: C, 54.17;
H, 5.38.
1
1. H-NMR(CDCl3): l 2.05 (s, C6Me6), 3.06 (s, MeO),
5.30 (s,ꢀCH), 5.7–7.6 (m, Ph) ppm. 31P{1H}-NMR
(CDCl3): l 173.6 (s), −143.8 (sep. JPF=709 Hz, PF6)
ppm. Anal. Calc. for C36.25H41.5O3Cl0.5PRu: C, 57.70;
H, 4.22. Found: C, 56.99; H, 4.66.
2.2. X-ray
2.2.1. Data collection
Complexes (6b, 7a, and 7e) were recrystallized from
CH2Cl2/hexane or CH2Cl2/ether. Cell constants were
determined on a Rigaku AFC5S four-circle automated
diffractometer from the setting angles of 20–25 reflec-
tions in the range from 20.0°B2qB30.0°. The crystal
parameters along with data collection details are sum-
marized in Table 1. Data collection was carried out on
a Rigaku AFC5S diffractometer. Intensities were mea-
sured by the 20-co scan method using Mo–Kh radiation
2.1.11. Reaction of 1 with PhCꢁCH in the presence of
NaPF6 in CH2Cl2/MeOH
To a mixture of 1 (62 mg, 0.102 mmol) and PhCꢁCH
(0.25 ml) in CH2Cl2 (10 ml) and MeOH (5 ml) was
added NaPF6 (25 mg, 0.15 mmol) at room temperature.
After 15 h, the solvent was removed at reduced pressure
and the residue was recrystallized from CH2Cl2 and
Et2O to give 9a·12CH2Cl2 (91 mg, 46.6%) as orange
crystals. IR(Nujol): 841 (PF6) cm−1. UV-vis (CH2Cl2):
−1
˚
(u=0.71069 A). Scan rates of 8° min
for 6b, 16°
min−1 for 7a and 8° min−1 for 7e were used, respec-
tively. Throughout the data collection the intensities of
the three standard reflections were measured every 150
reflections as a check of the stability of the crystals and
no decay was observed.
1
umax 476 (log m 2.72) nm. H-NMR (CDCl3): l 1.83 (s,
C6Me6), 3.31 (s, MeO), 3.70 (s, MeO), 3.97, 4.02 (s,
CH2), 5.3–7.7 (m, Ph) ppm. 31P{1H}-NMR (CDCl3): l
56.0 (s), 142.9 (sep. JPF=708 Hz, PF6) ppm. Anal.
Calc. for C40.5H45O3F6ClP2Ru: C, 54.52; H, 5.08.
Found: C, 54.83; H, 5.27.
A total of 7010 independent intensities (2qB50°) was
measured for 6b, 5707 (2qB50°) for 7a, and 5116
(2qB50°) for 7e, respectively. Of these, there are, re-
spectively, 4064, 1836 and 3270 (I\3.0|(I)) unique
reflections which were used in the solutions and refine-
ments of the structures. Intensities were corrected for
Lorentz and polarization effects and for absorption.
Atomic scattering factors and anomalous dispersion
effects were taken from the usual tabulation [6].
Anomalous dispersion effects were included in Fcalc [7];
the values of Df% and Df%% were from Creagh and
McAuley [8]. All calculations were performed on a
Digital VAX Station 3100 M38 computer using the
TEXSAN-TEXRAY program system.
2.1.12. Reaction of 1 with Me2C(OH)CꢁCH in the
presence of NaPF6 in CH2Cl2/MeOH
To a mixture of 1 (59.7 mg, 0.099 mmol) and
HCꢁCCMe2(OH) (0.25 ml) in CH2Cl2 (20 ml) and
MeOH (10 ml) was added NaPF6 (25 mg, 0.15 mmol)
at room temperature. After 2.5 h, the solvent was
removed at reduced pressure and the residue was re-
crystallized from CH2Cl2 and Et2O gave 10c (18.9 mg,
23.6%) as orange crystals. IR(Nujol): 1640 (CꢀC), 841
1
(PF6) cm−1. UV-vis (CH2Cl2): umax 339 nm. H-NMR
(CDCl3): l 1.37, 1.41 (s, ꢀCMe2), 1.91 (s, C6Me6), 3.32
(s, MeO), 3.68 (s, MeO), 4.62 (s, ꢀCH), 5.9–7.6 (m,
Ph). 31P{1H}-NMR (CDCl3): l 56.5 (s), 143.8 (sep.
Fig. 1. Possible structure of 2.
Fig. 2. Structure of 4 and 5.

34
Y. Yamamoto et al. / Journal of Organometallic Chemistry 569 (1998) 29–37
Scheme 3.
taining monophosphine ligands were substituted readily
with various Lewis bases in the presence of large anions
to form the [(p6-arene)RuCl(PR3)(L)]+ complexes [9].
Analogous reactions were carried out for the P–O
chelated complexes. Reaction of (p6-C6Me6)RuCl-
(MDMPP-P,O) 1 with carbon monoxide did not occur
at room temperature, whereas on heating under a high
pressure of CO the arene ring was eliminated to give
[RuCl(MDMPP-P,O)(CO)3] 2. The infrared spectrum
showed three peaks at 2058, 1986, and 1946 cm−1 due
to terminal carbonyl groups. Three kinds of structures
are assumed for 2. Based on the fact that the arene ring
occupies three cis-sites of an octahedral configuration,
the facial structure (A) are assumed to be superior to
two other meridional ones (B and C) (Fig. 1). A similar
elimination of the arene ring occurred in (p6-p-
2.2.2. Determination of the structures
The structures were solved by direct methods with
MITHRIL for 6b and 7a and Patterson methods for 7e.
The ruthenium atom was located in the initial E map,
and subsequent Fourier syntheses gave the positions of
other non-hydrogen atoms. Hydrogen atoms were cal-
culated at the ideal positions with the C–H distance of
˚
0.95 A, and were not refined. The non-hydrogen atoms
were refined with anisotropic thermal parameters by
using full-matrix least-squares methods. Final differ-
ence Fourier syntheses showed peaks at heights up to
−3
˚
0.44–0.73 eA
.
3. Results and discussion
cymene)Ru(BDMPP-P,O,O)
3
to give [Ru(CO)3
Overall reactions described here are depicted in
Scheme 1 and Scheme 2.
(TDMPP-P,O,O)] 4. The infrared spectrum showed the
presence of three carbonyl groups, also suggesting a
facial structure as well as that of 2 (Fig. 2). When an
analogous reaction was carried out in the presence of
xylyl isocyanide, the complex [Ru(CO)2(XylNC)
(TDMPP-P,O,O)] 5 was obtained as an only isolated
3.1. Reactions with Lewis bases
It has been known that halogens of the
(arene)ruthenium complexes (p6-arene)RuCl2(PR3) con-
Fig. 3. Molecular structure of 6b (PF6 was omitted for clarity).
Fig. 4. Molecular structure of 7a.

Y. Yamamoto et al. / Journal of Organometallic Chemistry 569 (1998) 29–37
35
to a w(CO) or w(NC) band, respectively. The 31P{1H}-
nmr spectrum of 6a appeared at the lower field by l 1.6
ppm than that (l 52.0 ppm) of 6b, responsible for the
higher |-donor ability of isocyanide than carbon
monoxide.
3.2. Metal acetylides and their related complexes
Metal vinylidene and related unsaturated carbene
species play an important role in Fisher-Tropsch chem-
istry [10]] and in acetylene polymerization [11]. They
can be synthesized from metal aklynyl complexes [12].
When 1 in CH2Cl2/methanol was treated with phenyl
acetylene in the presence of triethylamine or methanolic
potassium hydroxide, orange yellow crystals of [(p6-
C6Me6)Ru(CꢁCPh)(MDMPP-P,O)] 7a were isolated.
The infrared spectrum showed a peak at 2089 cm−1
Fig. 5. Molecular structure of 7e.
1
due to the w(CꢁC) band. The H-nmr spectrum showed
product from the mass spectrum and elemental analy-
sis. The infrared spectrum showed three characteristic
bands at 2176 (NꢁC), 2031 and 1970 (CꢁO) cm−1. Two
possible structures (A and B) are considered, but the
detailed structure is kept unknown (Fig. 2). Elimination
of an arene ligand has been observed in the reaction of
[(p6-p-cymene)RuCl2]2 with MDMPP at room tempera-
ture to give [RuCl2(MDMPP-P,OMe) [4].
When 1 was treated with CO or xylyl isocyanide in
the presence of NH4PF6 at room temperature, yellow
crystals formulated as [(p6-C6Me6)Ru(MDMPP-
P,O)(L)](PF6) (6a: L=CO, 6b: L=XylNC) were ob-
tained, respectively. The infrared spectra showed a
band at 2004 cm−1 for 6a and at 2135 cm−1 for 6b due
two singlets at l 1.91 and 3.03 ppm assignable to the
methyl and methoxy groups, respectively. The 31P{1H}-
NMR spectrum showed a singlet at l 58.1 ppm. The
reaction with methyl propiolate also gave the acetylide
complex 7b. The infrared spectrum showed two charac-
teristic bands at 2081 and 1669 cm−1, due to the
1
w(CꢁC) and w(CꢀO) bands, respectively. The H-NMR
spectrum showed three bands at l 1.88, 3.27 and 3.30
ppm in a 6:1:1 intensity ratio, assignable to methyl,
methoxy and methoxycarbonyl groups, respectively.
Analogous acetylide complexes 7, [(p6-C6Me6)Ru(Cꢁ
CR)(MDMPP-P,O)] (c: R=C(Me)2OH; d: R=
CH(Me)OH; e=CH2OH) were obtained from the reac-
tions with the corresponding propargyl alcohol
Table 2
˚
Selected bond lengths (A) and angles (°) of 6b
Bond length
Rul–P1
O1–C26
Cl–N1
2.318(2)
1.357(9)
1.138(7)
Ru1–O2
O1–C27
Ru–Ca*v
2.070(4)
1.421(9)
2.257(8)
Rul–C1
O2–C22
1.940(7)
1.314(7)
Bond angle
Pl–Ru1–O2
O2–Rul–C1
Rul–Pl–C21
Cl–Nl–C11
82.4(1)
85.1(2)
99.5(2)
171.8(6)
Pl–Rul–C1
Ru1–O2–C22
Rul–Cl–N1
84.7(2)
120.2(4)
175.2(6)
Table 3
˚
Selected bond lengths (A) and angles (°) of 7a
Bond length
Rul–P1
O1–C12
C1–C2
2.298(4)
1.32(1)
1.19(2)
Ru1–O1
O2–C16
Rul–Ca*v
2.095(8)
1.38(2)
2.25(1)
Rul–C1
O2–C17
1.99(l)
1.38(1)
Bond angle
Pl–Ru1–O1
O1–Rul–C1
Rul–Pl–C11
C1–C2–C3
82.0(3)
84.6(5)
101.5(5)
Pl–Rul–C1
Ru1–O1–C12
Rul–Cl–C2
81.8(4)
120.6(9)
177(1)
174(2)

36
Y. Yamamoto et al. / Journal of Organometallic Chemistry 569 (1998) 29–37
Table 4
˚
Selected bond lengths (A) and angles (°) of 7e
Bond length
Rul–P1
O2–C32
O3–C3
2.296(2)
1.317(6)
1.396(8)
Ru1–O1
O2–C36
C1–C2
2.090(4)
1.366(6)
1.192(7)
Rul–C1
O2–C37
Ru–Ca*v
2.009(6)
1.390(7)
2.249(5)
Bond angle
Pl–Ru1–O1
O1–Rul–C1
Ru1–O1–C32
C1–C2–C3
82.1(1)
82.7(2)
120.0(3)
177.8(7)
Pl–Rul–C1
Rul–Pl–C31
Rul–Cl–C2
84.6(2)
101.6(2)
170.8(5)
due to two vinylic methyl and methyl groups of the
arene ring, the last one to a vinyl proton, the others to
methoxy group of phosphine and h-substituted
methoxy one, respectively.
The reaction consists of an initial formation of an
acetylene complex, followed by rearrangement of a
proton to form a vinylidene complex and by the forma-
tion of an allenylidene intermediate via a subsequent
elimination of H2O [13]. The final metallabutadiene
complex is completed by the 1,2-addition of MeOH to
the intermediate (Scheme 3).
derivatives. The structures of these complexes were
confirmed by an X-ray analysis of 7e (vice infra). The
31P{1H}-NMR spectrum of 7d showed two singlets at l
58.1 and 58.4* ppm consisting of an intensity ratio 45:
55, suggesting the diastereomers derived from two chi-
1
ral centers. The H-NMR spectrum also supported the
presence of two isomers. It consists of a well-defined
pair for each of the methyl protons of the arene,
acetylide and mehthoxy groups; each pair is l 1.86 (s)
and 1.87 (s)* ppm, 0.81* (d, JHH=6.3 Hz) and 1.40 (d,
J
HH=6.3 Hz) ppm, and 3.26 (s) and 3.27 (s)* ppm,
respectively.
3.3. Structures of 6b, 7a, and 7e
When 1 was treated with phenylacetylene in CH2Cl2/
acetone in the presence of NaPF6, the orange complex
formulated as [(p6-C6Me6)Ru(MDMPP-P,O)(ꢀCꢀCH-
Ph)](PF6) 8a was isolated. The infrared spectrum
All complexes display a piano-stool structure which a
Ru atom was coordinated by phosphorus, oxygen and
carbon atoms and an arene ring (Figs. 3–5). The
selected bond lengths and angles were shown in Table
2, Table 3 and Table 4. The Ru–P bond length of 6b is
somewhat longer than those found in the alkynyl com-
showed a CꢀC double bond at 1620 cm−1. The H-
1
NMR spectrum showed three singlets at l 2.05, 3.06
and 5.30 ppm, assignable to methyl, methoxy and
vinylidene protons. The 31P{1H}-NMR spectrum
showed a singlet at l 173.6 ppm. When the reaction
was carried out in MeOH, a carbene complex [(p6-
C6Me6)Ru(MDMPP-P,O){ꢀC(OMe)(CH2Ph)}](PF6) 9a
was isolated. The 1H-NMR spectrum showed three
singlets at l 1.83, 3.32 and 3.70 ppm, due to one methyl
and two methoxy protons. The reaction of 1 with
Me2C(OH)CꢁCH in the presence of NaPF6 in MeOH
gave orange crystals 10c formulated as [(p6-
C6Me6)Ru(MDMPP-P,O) {ꢀC(OMe)CHꢀCMe2}](PF6)
in 24% yield. In the infrared spectrum the peak due to
the double bond appeared at 1640 cm−1 and the pres-
ence of the P–O chelation was confirmed by two peaks
at 1582 and 1547 cm−1 ]. The spectral pattern of the
1H-NMR spectrum is similar to that of the metallabu-
tadiene complex [(p6-1,2,3,4-Me4C6H2)RuCl(PMe3)
{ꢀC(OMe)CHꢀCMe2}](PF6) obtained from the reaction
of (p6-1,2,3,4-Me4C6H2)RuCl2(PMe3) with Me2C(OH)-
CꢁCH in the presence of NaPF6 in MeOH [13]. Thus,
˚
plexes 7. This difference of bond length (ca. 0.02 A) is
traced back to that of the Ru–O bond lengths, where
˚
˚
the bond length (2.070(4) A) in 6b is shorter by 0.02 A
˚
than those in 7. The Ru–C bond length (1.940(7) A) of
6b is shorter than those of 7a and 7e, responsible for
the difference of chemical bonding mode and the differ-
ence of back-bonding ability between 6 and 7. The
Ru–C–C, Ru–C–N, C–C–C and C–N–C bond an-
gles are not sign)ficantly different from linearity. The
˚
NꢁC triple bond length of 1.19(2) A is shorter than
those of the CꢁC triple bond, depending on the cova-
lent radii. The bite angles of three complexes are ca.
82°, not different from those of the starting and related
complexes [4].
4. Supplementary materials
Tables of atomic positional parameters, anisotropic
temperature factors, and bond lengths and angles, and
a listing of observed and calculated structure factors are
available from Y.Y. on request.
1
the H-NMR spectrum showed six singlets at l 1.37,
1.41, 1.91, 3.32, 3.68, and 4.62 ppm consisting of an
intensity ratio of 3:3:6:3:3:1; the first three peaks are

Y. Yamamoto et al. / Journal of Organometallic Chemistry 569 (1998) 29–37
37
[3] (a) E.Lindner, A. Bader, Coord. Chem. Rev. 108 (1991) 27. (b)
E. Lindner, M. Haustein, H.A. Mayer, K. Gierling, R. Fawzi,
M. Steimann, Organometallics 14 (1995) 2245. (c) E. Lindner,
H.A. Mayer, R. Fawzi, M. Steimann, Organometallics 12 (1993)
1865. (d) E. Lindner, M. Haustein, R. Fawzi, M. Steimann, P.
Wgner, Organometallics 13 (1994) 5021.
[4] (a) Y. Yamamoto, R. Sato, M. Ohshima, F. Matsuo, J.
Organomet. Chem. 489 (1995) C68. (b) Y. Yamamoto, R. Sato,
F. Matsuo, C. Sudoh, T. Igoshi, Inorg. Chem. 35 (1996) 2329.
[5] W.R. Hertler, E.J. Corey, J. Org. Chem. 23 (1958) 1221.
[6] D.T. Cromer, J.T. Waber, International Tables for X-ray Crys-
tallography, vol. IV, The Kynoch Press, Birmingham, 1974,
Table 2.2A.
Acknowledgements
We thank Professor Sigetoshi Takahashi and Fumie
Takei in the Institute of Scientific and Industrial Re-
search, Osaka University for measurement of FAB
mass.
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