Reaction of [RuCl2(DMSO)4] with aromatic phosphines bearing ortho-methoxy groups

Article abstract of DOI:10.1039/a906435d

Reaction of [RuCl₂(DMSO)₄] 1 with (2,6-dimethoxyphenyl)diphenylphosphine (MDMPP) in acetone-CH₂Cl₂ at reflux gave t,c,c-[RuCl₂(MDMPP-κ²P,O)₂] 2. Reaction with bis(2,6-dimethoxyphenyl)phenylphosphine (BDMPP) afforded the phosphonium salt containing a ruthenium(II) anion, [BDMPP(CH₂Cl)][RuCl₃(DMSO)₃] 3b, [BDMPP(CH₂Cl)][RuCl(DMSO)₂{PPh(C₆H ₃OMe-6-O-2)₂-κ³P,O,O′)] 4b and [BDMPP(CH₃)][RuCl (DMSO)₂{PPh(C₆H₃OMe-6-O-2) ₂-κ³P,O,O′)] 4d [BDMPP(CH₂Cl) = {2,6-(MeO)₂C₂H₃}₂PhP(CH ₂Cl), BDMPP(CH₃) = {2,6-(MeO)₂C₆H₃}₂PhP(CH ₃)]; complexes 4 contain tridentate P,O,O′ co-ordination in which two methoxy groups of BDMPP were demethylated. These structures were confirmed by X-ray analyses. Tris(2,6-dimethoxyphenyl)phosphine (TDMPP) reacted with 1 to give 3c [TDMPP-(CH₂Cl)][RuCl₃(DMSO)₃] [TDMPP(CH₂Cl) = {2,6-(MeO)₂ C₆H₃}₃P(CH₂Cl)]. Complex 2 reacted with xylyl or mesityl isocyanide to give mer-[RuCl₂(MDMPP-P)(RNC)₃] 5. Reaction with CO afforded [RuCl₂(MDMPP-P)(MDMPP-κ²P,O)(CO)] 6 and an insoluble unidentified complex. The structure of 6 was confirmed by an X-ray analysis; one MDMPP group acts as a P,O bidentate ligand, the other as a monodentate ligand, and a CO ligand occupies the trans position to an oxygen atom. Two Cl and two P atoms were located at mutually trans positions. The phosphonium salt [BDMPP(CH₂Cl)]Cl, derived from CH₂Cl ₂ and BDMPP, reacted with 1 to afford 3b. The reaction of 3b with BDMPP gave 4b and 4d. The reaction pathways are discussed. The Royal Society of Chemistry 1999.

Full text of DOI:10.1039/a906435d

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Reaction of [RuCl2(DMSO)4] with aromatic phosphines bearing
ortho-methoxy groups†
Yasuhiro Yamamoto,* Ken-ichiro Sugawara, Tsuyoshi Aiko and Jian-Fang Ma
Department of Chemistry, Faculty of Science, Toho University, Miyama 2-2-1, Funabashi,
Chiba 274-8510 Japan. E-mail: yamamoto@chem.sci.toho-u.ac.jp
Received 9th August 1999, Accepted 5th October 1999
Reaction of [RuCl2(DMSO)4] 1 with (2,6-dimethoxyphenyl)diphenylphosphine (MDMPP) in acetone–CH2Cl2
at reflux gave t,c,c-[RuCl2(MDMPP-κ2P,O)2] 2. Reaction with bis(2,6-dimethoxyphenyl)phenylphosphine
(BDMPP) afforded the phosphonium salt containing a ruthenium() anion, [BDMPP(CH2Cl)][RuCl3(DMSO)3]
3b, [BDMPP(CH2Cl)][RuCl(DMSO)2{PPh(C6H3OMe-6-O-2)2-κ3P,O,OЈ)] 4b and [BDMPP(CH3)][RuCl
(DMSO)2{PPh(C6H3OMe-6-O-2)2-κ3P,O,OЈ)] 4d [BDMPP(CH2Cl) = {2,6-(MeO)2C2H3}2PhP(CH2Cl),
BDMPP(CH3) = {2,6-(MeO)2C6H3}2PhP(CH3)]; complexes 4 contain tridentate P,O,OЈ co-ordination in
which two methoxy groups of BDMPP were demethylated. These structures were confirmed by
X-ray analyses. Tris(2,6-dimethoxyphenyl)phosphine (TDMPP) reacted with 1 to give 3c [TDMPP-
(CH2Cl)][RuCl3(DMSO)3] [TDMPP(CH2Cl) = {2,6-(MeO)2 C6H3}3P(CH2Cl)]. Complex 2 reacted
with xylyl or mesityl isocyanide to give mer-[RuCl2(MDMPP-P)(RNC)3] 5. Reaction with CO afforded
[RuCl2(MDMPP-P)(MDMPP-κ2P,O)(CO)] 6 and an insoluble unidentified complex. The structure of 6 was
confirmed by an X-ray analysis; one MDMPP group acts as a P,O bidentate ligand, the other as a monodentate
ligand, and a CO ligand occupies the trans position to an oxygen atom. Two Cl and two P atoms were located at
mutually trans positions. The phosphonium salt [BDMPP(CH2Cl)]Cl, derived from CH2Cl 2 and BDMPP, reacted
with 1 to afford 3b. The reaction of 3b with BDMPP gave 4b and 4d. The reaction pathways are discussed.
Tris(2,4,6-trimethoxyphenyl)phosphine (TMPP) bearing meth-
oxy groups at the 2,4 and 6 positions of the phenyl groups
exhibits high basicity and nucleophilicity.1–3 The transition
metal chemistry of this phosphine has been studied by
Dunbar’s group.4 It can act as a mono-, bi- and tri-dentate
ligand. The reaction of a square-planar complex [Pd(NC-
CH3)4][BF4]2 with TMPP gave a pseudo-octahedral complex
[Pd(TMPP-κ3P,O,OЈ)2][BF4]2 defined by two phosphorus and
two ether-oxygen atoms in an equatorial arrangement, and two
ether-oxygen atoms in axial sites.5a The reaction of the six-
co-ordinate complex [Ni(NCCH3)6][BF4]2 and TMPP gave a
square-planar complex cis[Ni(TMPP-κ2P,O)2] in which the
metal atom is surrounded by two phosphorus atoms and two
phenoxide-O atoms.6 Recently, palladium and platinum analogs
of the four-co-ordinate nickel complex have been isolated.5b
We have been interested in the reactions of aromatic
phosphines bearing methoxy groups at 2,6 positions with
transition metal complexes. Aromatic phosphines such as
(2,6-dimethoxyphenyl)diphenylphosphine (MDMPP), bis(2,6-
dimethoxyphenyl)phenylphosphine (BDMPP), and tris(2,6-
dimethoxyphenyl)phosphine (TDMPP) show a variety of
reactivity similar to that of TMPP. We have reported that reac-
tions of bis[(η6-arene)dichlororuthenium()] or bis[dichloro(η5-
pentamethylcyclopentadienyl)rhodium()] with MDMPP,
BDMPP or TDMPP gave various types of complexes bearing a
P, ether-O [(κ2P,O) or (κ3P,O,OЈ)] and phenoxide-O co-
ordination [(κ2P,O) or (κ3P,O,OЈ)], depending on the com-
plexes, phosphines and reaction conditions.7,8
m-xylenediamine bis(Kemp’s triacid imide)]10 gave [Ru2(µ-Cl)-
(µ-H)(µ-DMSO-S,O)Cl2(DMSO-S)4] in which one DMSO
acts as a S,O-bidentate ligand.11 We have been interested in
reactivities of the aforementioned bulky phosphines having high
basicity towards octahedral metal complexes in relation with
the difference in co-ordination numbers found in acetonitrile
complexes of palladium and nickel.5a,6 We found that the octa-
hedral complex [RuCl2(DMSO)4] 1 reacted readily with these
phosphines in CH2Cl2 to generate the [RuCl3(DMSO-S)3]Ϫ
anion as the phosphonium salt. This reaction provides a method
to convert neutral complexes into anionic ones.
Experimental
All reactions were carried out under a nitrogen atmosphere.
Complex 1,12 phosphines (MDMPP, BDMPP and TDMPP),1
isocyanides13 and phosphonium salts1b ([BDMPP(CH2Cl)]Cl,
[BDMPP(CH3)]Cl, and [TDMPP(CH2Cl)]Cl) were prepared
according to the literature methods. Dichloromethane was dis-
tilled from CaH2 and diethyl ether from LiAlH4. Other reagents
were available commercially. The infrared and electronic
absorption spectra were measured on FT/IR-5300 and U-best
30 spectrometers, respectively, 1H (250 MHz) and 31P-{1H}
NMR spectra using 85% H3PO4 as external reference on a
Bruker AC250, and fast atom bombardment (FAB) mass
spectra on a JMS-DX300 spectrometer.
Reactions of complex 1
Transition-metal complexes of dimethyl sulfoxide (DMSO)
are useful starting materials for many inorganic and organo-
metallic compounds.9 Recently we have reported that [RuCl2-
(DMSO)4] in the presence of Na2(xdk)4ؒH2O [H2xdk =
With MDMPP. A mixture of complex 1 (72 mg, 0.15 mmol)
and MDMPP (208 mg, 0.65 mmol) was refluxed in acetone–
CH2Cl2 (1:1 ratio, 40 mL). After 1.5 h the solvent was removed
to ca. 5 ml and diethyl ether added to form reddish violet crys-
tals of t,c,c-[RuCl2(MDMPP-κ2P,O)2] 2 (31.4 mg, 26%), which
were identified by comparison with spectroscopic data of an
authentic sample.7
† Supplementary data available: rotatable 3-D crystal structure diagram
in CHIME format. see http://www.rsc.org/suppdata/dt/1999/4003/
J. Chem. Soc., Dalton Trans., 1999, 4003–4008
This journal is © The Royal Society of Chemistry 1999
4003

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With BDMPP. A mixture of complex 1 (72 mg, 0.15 mmol)
and BDMPP (85 mg, 0.22 mmol) was stirred in CH2Cl2 (20 mL)
at room temperature. After 4 h the solvent was removed and the
residue recrystallized from CH2Cl2 and diethyl ether to give
yellow crystals of [BDMPP(CH2Cl)][fac-RuCl3(DMSO-S)3] 3b
(87 mg, 67%). The further recrystallization of the mother-
liquor gave white crystals of [BDMPP(CH2Cl)][RuCl(DMSO-
S)2{PPh(C6H3OMe-6-O-2)2-κ3P,O,OЈ}] 4b (15.3 mg, 10%)
and [BDMPP(CH3)][RuCl(DMSO-S)2{PPh(C6H3OMe-6-O-
2)2-κ3P,O,OЈ}] 4d (2 mg) [BDMPP(CH3) = PPh{2,6-(MeO)2-
C6H3}2(Me)]. Complex 3b: FAB MS m/z 431 (Mϩ of a cation);
1H NMR(CDCl3) δ 3.54 (s, DMSO, 18 H), 3.62 (s, OMe, 12 H),
4.86 (d, JPH = 6.3 Hz, CH2, 2 H) and 6.75–7.80 (m, Ph, 22 H);
31P-{1H} NMR(CDCl3) δ 14.92 (s) (Calc. for C29H43Cl4O7-
PRuS3: C, 39.86; H, 4.96; Cl, 16.23; S, 11.01. Found: C, 39.06;
H, 4.73; Cl, 15.49; S, 11.30%). Complex 4b: FAB MS: m/z 431
(Mϩ of a cation); 1H NMR(CDCl3) δ 2.56 (s, MeS, 3 H), 2.72 (s,
MeS, 3 H), 2.96 (s, MeS, 3 H), 3.26 (s, MeS, 3 H), 3.41 (s, MeO,
3 H in an anionic species), 3.48 (s, MeO, 3 H in an anionic
species), 3.58 (s, MeO in a cationic species, 12 H), 4.89 (d,
JPH = 6.5 Hz, PCH2, 2 H) and 5.85–7.80 (m, Ph, 22 H); 31P-{1H}
NMR(CDCl3) δ 14.96 (s, phosphonium, 1P) and 67.8 (s). Com-
According to the above procedures, the mesityl isocyanide
complex, mer-[RuCl2 (MDMPP-P)(MesNC)3] 5b (45%) was
obtained from the reaction of 2 with mesityl isocyanide
(MesNC). IR(Nujol) 2170 and 2110 cmϪ1 N(᎐C). UV-
᎐
᎐
vis(CH2Cl2) λmax 324 nm. 1H NMR(CDCl3) δ 2.23 (s, o-Me, 18
H), 2.24 (s, p-Me, 3 H), 2.48 (s, p-Me, 3 H), 3.06 (s, OMe, 6 H)
31
and 6.43–8.22 (m, Ph, 19 H). P-{1H} NMR(CDCl3) δ 21.83
(s). Calc. for C50H52Cl2N3O2PRu: C, 64.58; H, 5.64; N, 4.52.
Found: C, 64.28; H, 5.56; N, 4.34%.
With CO. Into a solution of complex 2 (72 mg, 0.088 mmol)
in CH2Cl2 (35 mL) was bubbled carbon monoxide for 5 min at
room temperature. After 5.5 h the resulting white precipitate
(74.7 mg) was filtered off, and the filtrate concentrated to ca. 5
mL. Diethyl ether was added to give yellow crystals of
[RuCl2
(MDMPP-P)(MDMPP-κ2P,O)(CO)] 6 (4 mg, 6%). FAB
MS: m/z 844 (Mϩ) and 816 (M Ϫ COϩ). IR(Nujol) 1962 cmϪ1
(C᎐
᎐
O).
1H NMR (CD2Cl2) δ 3.53 (s, MeO, 12 H) and 6.6–8.1
᎐
(c, Ph, 23 H). 31P-{1H} NMR(CD2Cl2) δ 30.31 (br s, 1P). White
solid: IR(Nujol) 2010 and 1983 cmϪ1 (C᎐
O). Constant values
᎐
᎐
were not obtained in the elemental analysis.
1
plex 4d: H NMR(CDCl3) δ 2.56 (s, MeS, 3 H), 2.72 (s, MeS,
3 H), 2.96 (s, MeS, 3 H), 3.26 (s, MeS, 3 H), 3.41 (s, MeO, 3 H),
3.48 (s, MeO, 12 H), 2.58 (d, JPH = 14.2 Hz, PMe, 3 H), 3.57 (s,
Crystallography
Complexes 3b, 4b, 5a, 5b and 6 were recrystallized from
CH2Cl2–diethyl ether. The crystal parameters along with data
collection are summarized in Table 1. Data intensities were
measured by the 2θ–ω scan method using graphite-mono-
chromated Mo-Kα radiation (λ = 0.71069 Å) at 27Њ and
corrected for Lorentz-polarization effects. No decay was
observed. Absorption corrections were made with empirical
ψ scans. Atomic scattering factors were taken from Cromer
MeO in a phosphonium species, 12 H), 5.27 (s, CH2Cl ) and
2
5.75–7.80 (m, Ph, 22 H); 31P-{1H} NMR(CDCl3) δ 8.64 (s,
phosphonium, 1P) and 67.8 (s, an anion, 1P) (Calc. for
C49H61ClO10P2RuS2ؒ1.5CH2Cl2: C, 50.54; H, 5.37. Found: C,
50.82; H, 5.38%).
With TDMPP. A mixture of complex 1 (73 mg, 0.15 mmol)
and TDMPP (151 mg, 0.34 mmol) was stirred in CH2Cl2 (10
mL) at room temperature. After 1.5 h the work-up of the reac-
tion mixture and recrystallization from CH2Cl2 and diethyl
ether gave yellow crystals of [TDMPP(CH2Cl)][ fac-RuCl3-
(DMSO-S)3] 3c (69 mg, 71%). FAB MS m/z 491 (Mϩ of a
and Waber.14 Anomalous dispersion effects were included in
15
Fcalc
;
the values of ∆f Ј and ∆f Љ were those of Creagh and
McAuley.16 All calculations were performed using the TEXSAN
crystallographic software package.17
All structures were solved by Patterson methods (DIRDIF
92)18 and refined by full-matrix least-squares methods. All non-
hydrogen atoms were refined anisotropically, and hydrogen
atoms were calculated at the ideal positions with C–H distances
of 0.95 Å.
CCDC reference number 186/1676.
See http://www.rsc.org/suppdata/dt/1999/4003/ for crystallo-
graphic files in .cif format.
1
cation). H NMR(CDCl3) δ 3.55 (s, DMSO, 18 H), 3.60 (s,
OMe, 18 H), 4.86 (d, JPH = 7.0 Hz, CH2, 2 H), 6.6 (m, m-H, 6 H)
and 7.56 (t, p-H, 3 H). 31P-{1H} NMR(CDCl3) δ 9.99 (s). Calc.
for C31H47Cl4O9PRuS3: C, 39.87; H, 5.07. Found: C, 39.46;
H, 4.97%.
With [TDMPP(CH2Cl)]Cl. A mixture of complex 1 (144.3
mg, 0.30 mmol) and phosphonium salt 5c (292.4 mg, 0.59
mmol) was stirred in CH2Cl2 at room temperature. After 3 h the
solution was concentrated to ca. 3 mL and diethyl ether added
to yield yellow crystals of 3c (220 mg, 79%). Compound 3b was
prepared from 1 and [BDMPP(CH2Cl)]Cl in a similar manner.
Results and discussion
Reactions in dichloromethane
When [RuCl2(DMSO)4] 1 was treated with four equivalents of
MDMPP in CH2Cl2 1 was recovered quantitatively, but the
reaction in refluxing acetone–CH2Cl2 gave the known reddish
violet compound t,c,c-[RuCl2(MDMPP-κ2P,O)2] 2 (Scheme 1).7
A similar reaction of 1 with BDMPP in a 1:2 molar ratio in
CH2Cl2 at room temperature afforded a yellow compound
(main product) formulated as [BDMPP(CH2Cl2)] [RuCl3-
(DMSO-S)3] 3b in addition to two white complexes (minor
Reaction of complex 3b with BDMPP
A mixture of complex 3b (50.6 mg, 0.06 mmol) and BDMPP
(100 mg, 0.26 mmol) was refluxed in MeOH (20 mL) for 3 h.
The solution was concentrated to ca. 3 mL and diethyl ether
added to give white crystals of 4d (33.3 mg, 53.6%) and a small
amount of 4b.
products),
[BDMPP(CH2Cl)][RuCl(DMSO-S)2{PPh(C6H3-
OMe-6-O-2)2-κ3P,O,OЈ}] 4b and [BDMPP(CH3)] [RuCl-
(DMSO-S)2{PPh(C6H3OMe-6-O-2)2-κ3P,O,OЈ)}] 4d. The FAB
mass spectroscopy of 3b and 4b showed the same molecular
peak at m/z 431 which was consistent with the presence of
[BDMPP(CH2Cl)]ϩ. The 1H NMR spectrum of 3b showed two
singlets at δ 3.54 and 3.62, and a doublet at δ 4.86, in a 18:12:2
intensity ratio, assignable to DMSO, methoxy and methylene
groups, respectively. In the 31P-{1H} NMR spectrum only one
peak appeared at δ 14.92. These spectroscopic data suggested a
salt-like compound [BDMPP(CH2Cl)][RuCl3(DMSO-S)3]. The
stereochemistry was confirmed by an X-ray analysis (Fig. 1). A
similar conversion into a metal complex anion has been noted
in the reaction of iron() chloride with TMPP to afford
Reactions of complex 2
With 2,6-Xylyl isocyanide (XylNC). A mixture of complex 2
(73 mg, 0.089 mmol) and XylNC (42 mg, 0.32 mmol) was
stirred in CH2Cl2 (20 mL) at room temperature. After 6 h the
solvent was removed to ca. 5 mL and diethyl ether added to
form yellow crystals of mer-[RuCl2(MDMPP-P)(XylNC)3] 5a
(39 mg, 49%). IR(Nujol): 2168 and 2110 cmϪ1 (N᎐C). UV-
᎐
᎐
vis(CH2Cl2) λmax 324 nm. 1H NMR(CDCl3) δ 2.30 (s, o-Me, 12
H), 2.54 (s, o-Me, 6 H), 3.05 (s, OMe, 6 H) and 6.43–8.23 (m,
Ph, 22 H). 31P-{1H} NMR(CDCl3) δ 21.40 (s). Calc. for
C47H46Cl2N3O2PRu: C, 63.58; H, 5.22; N, 4.73. Found: C, 63.62;
H, 5.16; N, 4.78%.
4004
J. Chem. Soc., Dalton Trans., 1999, 4003–4008

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Table 1 Crystal data of [BDMPP(CH2Cl)][fac-RuCl3(DMSO-S)3] 3b, [BDMPPCH2Cl)][RuCl(DMSO-S)2{PPh(C6H3OMe-6-O-2)2-κ3P,O,OЈ}] 4b,
[RuCl2(MDMPP)(XylNC)3] 5a, [RuCl2(MDMPP)(MesNC)3] 5b and [RuCl2(MDMPP)(MDMPP-κ2P,O)(CO)] 6
3b
4b
5a
5b
6
Formula
M
C29H43Cl4O7PRuS3
873.69
C48H59Cl4O10P2RuS2
1164.94
C47H46Cl2N3O2Ru
887.85
C50H52Cl2N3O2PRu
929.23
C42H40Cl4O5P2Ru
929.60
Space group
a/Å
b/Å
c/Å
α/Њ
β/Њ
P21 (no. 4)
13.824(3)
9.671(3)
P1 (no. 2)
14.253(3)
16.592(3)
12.623(3)
102.13(2)
110.07(2)
102.09(2)
2609(1)
P21/n (no. 14)
11.441(5)
19.851(3)
P21 (no. 4)
11.667(3)
20.205(4)
P1 (no. 2)
13.70(1)
14.555(9)
12.346(7)
101.25(5)
114.69(5)
68.35(5)
2075(2)
15.292(2)
19.068(3)
19.932(4)
112.35(1)
83.17(2)
93.17(2)
γ/Њ
V/Å3
1890.8(9)
2
9.46
4323(2)
4
5.64
4691(1)
4
5.23
Z
2
7.01
2
7.55
µ/cmϪ1
R, RЈ (reflections
0.037, 0.041 (for 2858) 0.051, 0.064 (for 4831) 0.048, 0.065 (for 2846) 0.053, 0.111 (for 4334) 0.073, 0.098 (for 5251)
Scheme 1 Reactions of complex 1 with MDMPP, BDMPP and TDMPP; POMe = MDMPP; OPO = PPh{(2-O-6-MeO)2C6H3}2.
unexpectedly the dinuclear iron() chloride anion [Fe2Cl6]2Ϫ as
the phosphonium salt [{2,4,6-(MeO)3C6H2}3 PH]ϩ.19
excess of BDMPP in MeOH to produce 4d as the main product
and 4b as the minor one, suggesting the occurrence of cation
exchange between [BDMPP(CH2Cl)]ϩ and [BDMPP(CH3)]ϩ.
These results can be explained as follows. The reaction starts
with the formation of the phosphonium salt, derived from
BDMPP and CH2Cl2, and subsequently leads to 3b by a nucleo-
philic attack of a Cl anion on the ruthenium atom of 1. Com-
pound 3b reacts with an excess of phosphine to liberate two
CH3Cl molecules and is finally converted into 4b.
The formation of the phosphonium salt is assumed to be a
driving force for these reactions, which do not occur in acetone.
The reactions of TDMPP, BDMPP or MDMPP with CH2Cl2
are known to form the corresponding phosphonium salts,
[XDMPP(CH2Cl)]Cl (X = M, B or T). The half-lives increase in
the order of TDMPP, BDMPP and MDMPP, being 57, ca. 750
and 3740 min at 23 ЊC, respectively.20 Since the formation of the
phosphonium salt of MDMPP is very slow, the replacement of
DMSO with phosphine proceeded to give 2 before the forma-
tion of a phosphonium salt, but 3c was isolated exclusively
because of the easy formation of the phosphonium salt. For
BDMPP the formation of the phosphonium salt and the con-
version of the resulting 3b into 4b are considered to occur
concomitantly.
The 1H NMR spectrum of complex 4b showed seven singlets
at δ 2.56, 2.72, 2.96, 3.26, 3.41, 3.48 and 3.58, in a
1:1:1:1:1:1:4 intensity ratio, in the methyl region and a doub-
let at δ 4.89 due to a methylene group. The chemical shifts of the
resonances at δ 3.58 and 4.89 were in good agreement with
those found for [BDMPP(CH2Cl)]ϩ. The two resonances at δ
3.41 and 3.48 were tentatively assigned to the methoxy groups
and others to the DMSO ligands in the anionic species
[RuCl(DMSO-S)2{PPh(C6H3OMe-6-O-2)2-P,O,OЈ}].Sixmethyl
groups due to DMSO and the tridentate P,O,OЈ ligand were
inequivalent. The 31P-{1H} NMR spectrum showed two reson-
ances at δ 14.96 and 67.8 (s); the former was again similar to
that found for [BDMPP(CH2Cl)]ϩ.
The 1H NMR spectrum of the anionic species [RuCl(DMSO-
S)2PPh(C6H3OMe-6-O-2)2-κ2P,O,OЈ}] in 4d was in good agree-
ment with that found in 4b, whereas the resonances of a cat-
ionic species appeared at δ 2.58 due to the CH3(P) protons as a
doublet and at δ 3.57 due to the methoxy groups as a singlet,
being similar to those for [BDMPP(CH3)]Cl. Formation of 4d
showed that cation exchange had occurred.
Compound 1 reacted readily with TDMPP in CH2Cl2 at
room temperature to give only yellow crystals of [TDMPP-
CH2Cl][RuCl3(DMSO)3] 3c in high yield. The FAB mass
spectroscopy showed a molecular peak (m/z 491) of [TDMP-
Reactions of complex 2
When complex 2 was treated with XylNC or MesNC in reflux-
ing CH2Cl2, yellow crystals formulated as [RuCl2(MDMP-
P)(RNC)3] (R = Xyl; 5a or Mes 5b) were isolated (Scheme 1).
The IR spectra of 5 showed two bands at ca. 2170 and 2110
cmϪ1 due to the terminal isocyanide groups. The 1H NMR spec-
tra showed resonances due to two kinds of isocyanide groups in
a 1:2 intensity ratio. These spectroscopic data suggested a
meridional structure. The X-ray studies were in agreement with
the proposed structure (Figs. 3 and 4).
1
P(CH2Cl)]ϩ. The H NMR spectrum showed two singlets at
δ 3.55 and 3.60 and a doublet at δ 4.86 in a 18:18:2 inten-
sity ratio, assignable to the DMSO, methoxy and methylene
protons, respectively.
In attempts to examine the possible routes for formation of
complexes 3 and 4, the reaction of 1 with [BDMPP(CH2Cl)]Cl
was carried out at room temperature. It gave the corresponding
complex 3b in relatively high yield. Complex 3b reacted with an
J. Chem. Soc., Dalton Trans., 1999, 4003–4008
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Table 2 Selected bond lengths (Å) and angles (Њ) of [BDPMPP(CH2Cl)][RuCl3(DMSO-S)3] 3b and [BDPMPP(CH2Cl)][RuCl(DMSO)2-
{PPh(C6H3OMe-6-O-2)2-κ3P,O,OЈ}] 4b
Compound 3b
Ru–Cl(2)
Ru–S(1)
S(1)–O(5)
P–C(1)
2.420(2)
2.276(2)
1.452(6)
1.811(7)
1.829(6)
Ru–Cl(3)
Ru–S(2)
S(2)–O(6)
P–C(7)
2.438(2)
2.268(2)
1.472(5)
1.795(7)
Ru–Cl(4)
Ru–S(3)
S(3)–O(7)
P–C(15)
2.435(2)
2.263(2)
1.481(5)
1.800(7)
P–C(23)
Cl(2)–Ru–Cl(3)
Cl(2)–Ru–S(1)
Cl(2)–Ru–S(3)
Cl(3)–Ru–S(1)
Cl(3)–Ru–S(3)
Cl(4)–Ru–S(2)
86.41(6)
173.66(7)
93.10(7)
91.24(7)
87.31(7)
90.54(7)
Cl(2)–Ru–Cl(4)
Cl(2)–Ru–S(2)
Cl(3)–Ru–Cl(4)
Cl(3)–Ru–S(2)
Cl(4)–Ru–S(1)
Cl(4)–Ru–S(3)
88.43(7)
86.34(7)
89.86(7)
172.72(7)
85.67(7)
176.70(8)
S(1)–Ru–S(2)
S(2)–Ru–S(3)
C(1)–P–C(15)
C(7)–P–C(15)
C(15)–P–C(23)
96.03(7)
92.48(7)
113.4(3)
110.1(3)
104.1(3)
S(1)–Ru–S(3)
C(1)–P–C(7)
C(1)–P–C(23)
C(7)–P–C(23)
92.67(7)
111.5(3)
102.3(3)
115.1(3)
Compound 4b
Ru–P(1)
2.257(2)
2.482(2)
1.470(7)
1.315(7)
1.816(6)
1.818(6)
Ru–S(1)
Ru–O(2)
S(2)–O(6)
O(3)–C(9)
P(2)–C(33)
2.250(2)
2.089(4)
1.398(6)
1.379(8)
1.790(6)
Ru–S(2)
Ru–O(4)
O(1)–C(2)
O(4)–C(13)
P(2)–C(41)
2.216(2)
2.084(4)
1.364(7)
1.308(7)
1.791(7)
Ru–Cl(1)
S(1)–O(5)
O(2)–C(6)
P(2)–C(25)
P(2)–C(47)
Cl(1)–Ru–S(1)
Cl(1)–Rh–S(1)
Cl(1)–Ru–O(4)
(1)–Ru–P(1)
S(1)–Ru–O(4)
S(2)–Ru–O(2)
P(1)–Ru–O(2)
O(2)–Ru–O(4)
88.06(7)
165.96(6)
88.0(1)
99.06(7)
175.2(1)
176.4(1)
80.3(1)
Cl(1)–Ru–S(2)
Cl(1)–Ru–O(2)
S(1)–Ru–S(2)
S(1)–Ru–O(2)
S(2)–Ru–P(1)
S(2)–Ru–O(4)
P(1)–Ru–O(4)
Ru–O(2)–C(6)
91.55(6)
87.8(1)
94.75(6)
88.8(1)
99.84(6)
88.2(1)
84.2(1)
O(2)–C(6)–C(1)
Ru–P(1)–C(1)
O(4)–C(13)–C(8)
Ru–P(1)–C(8)
C(25)–P(2)–C(33) 108.7(3)
C(33)–P(2)–C(41) 110.4(3)
C(41)–P(2)–C(47) 103.9(3)
122.2(5)
102.3(2)
123.4(5)
101.2(2)
P(1)–C(1)–C(6)
Ru–O(4)–C(13)
P(1)–C(8)–C(13)
C(25)–P(2)–C(41) 114.5(3)
C(25)–P(2)–C(41) 114.5(3)
C(33)–P(2)–C(47) 113.5(3)
109.9(4)
118.5(3)
112.6(5)
88.3(1)
119.7(4)
Fig. 1 An ORTEP21 diagram of a cation and an anion of complex 3b
with thermal ellipsoids drawn at the 50% probability level (as in all
figures).
Fig. 2 An ORTEP diagram of a cation and an anion of complex 4b.
structure is unknown at present. The FAB mass spectrum of 6
showed a molecular peak at m/z 844 corresponding to
[RuCl2(MDMPP)2(CO)]. The IR spectrum showed a band at
1962 cmϪ1 assignable to a terminal carbonyl group. X-Ray crys-
tallographic analysis showed that one of the MDMPP groups
acts as a P,O-bidentate ligand and the other one as a monoden-
tate ligand (Fig. 5). The two phosphorus atoms and two chlor-
ine atoms are each mutually trans showing that a cis-to-trans
isomerization had occurred in the equatorial plane. This can be
Carbon monoxide was bubbled into a solution of complex 2
in CH2Cl2 for ca. 5 min at room temperature. A white precipi-
tate formed rapidly, and a small amount of yellow crystals 6
was isolated from the reaction solution (Scheme 1). The white
solid was insoluble in various solvents and its IR spectrum
showed the presence of terminal carbonyl bands (2010 and
1983 cmϪ1). The molecule is assumed to be polymeric but the
4006
J. Chem. Soc., Dalton Trans., 1999, 4003–4008

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Table 3 Selected bond lengths (Å) and angles (Њ) of mer-[RuCl2-
(MDMPP)(XylNC)3] 5a and mer-[RuCl2(MDMPP)(MesNC)3] 5b
Compound 5a
Compound 5b
Ru(1)–Cl(1)
Ru(1)–Cl(2)
Ru(1)–P(1)
Ru(1)–C(21)
Ru(1)–C(30)
Ru(1)–C(39)
C(21)–N(1)
C(30)–N(2)
C(39)–N(3)
2.434(2)
2.421(2)
2.401(2)
1.985(9)
1.966(9)
2.002(8)
1.162(10)
1.17(1)
Ru(1)–Cl(1)
Ru(1)–Cl(2)
Ru(1)–P(1)
Ru(1)–C(21)
Ru(1)–C(31)
Ru(1)–C(41)
C(21)–N(1)
C(31)–N(2)
C(41)–N(3)
2.423(2)
2.439(2)
2.408(2)
2.008(9)
1.967(9)
1.989(9)
2.008(9)
1.16(1)
1.146(9)
1.16(1)
Fig. 4 An ORTEP diagram of complex 5b.
Cl(1)–Ru(1)–Cl(2) 174.18(9)
Cl(1)–Ru(1)–Cl(2) 174.56(8)
Cl(1)–Ru(1)–P(1)
Cl(1)–Ru(1)–C(21)
Cl(1)–Ru(1)–C(30)
Cl(1)–Ru(1)–C(39)
Cl(2)–Ru(1)–P(1)
Cl(2)–Ru(1)–C(21)
Cl(2)–Ru(1)–C(30)
Cl(2)–Ru(1)–C(39)
P(1)–Ru(1)–C(21)
93.52(8)
92.0(2)
88.2(3)
93.1(2)
92.29(8)
87.5(2)
86.0(3)
87.0(2)
91.8(2)
Cl(1)–Ru(1)–P(1)
Cl(1)–Ru(1)–C(21)
Cl(1)–Ru(1)–C(31)
Cl(1)–Ru(1)–C(41)
Cl(2)–Ru(1)–P(1)
Cl(2)–Ru(1)–C(21)
Cl(2)–Ru(1)–C(31)
Cl(2)–Ru(1)–C(41)
P(1)–Ru(1)–C(21)
92.59(8)
88.1(2)
87.4(3)
86.9(3)
92.84(8)
92.0(2)
87.2(3)
92.4(3)
91.4(2)
P(1)–Ru(1)–C(30) 177.7(2)
P(1)–Ru(1)–C(39) 92.6(2)
P(1)–Ru(1)–C(31) 176.7(3)
P(1)–Ru(1)–C(41) 94.9(2)
C(21)–Ru(1)–C(30) 89.7(3)
C(21)–Ru(1)–C(39) 173.0(3)
C(30)–Ru(1)–C(39) 85.7(3)
Ru(1)–C(21)–N(1) 174.5(7)
C(21)–N(1)–C(22) 170.0(8)
Ru(1)–C(30)–N(2) 176.8(7)
C(30)–N(2)–C(31) 171.8(8)
Ru(1)–C(39)–N(3) 172.0(7)
C(39)–N(3)–C(40) 170.1(8)
C(21)–Ru(1)–C(31) 85.3(3)
C(21)–Ru(1)–C(41) 172.1(3)
C(31)–Ru(1)–C(41) 88.3(3)
Ru(1)–C(21)–N(1) 172.8(7)
C(21)–N(1)–C(22) 169.4(9)
Ru(1)–C(31)–N(2) 177.4(8)
C(31)–N(1)–C(32) 175.8(9)
Ru(1)–C(41)–N(3) 171.9(7)
C(41)–N(1)–C(42) 169.1(9)
Fig. 5 An ORTEP diagram of complex 6.
from demethylation of two methoxy groups of BDMPP. The Cl
atom is trans to the P atom (Fig. 2). The S–Ru–P and S–Ru–S
angles are ca. 99 and 95Њ, respectively. These larger than ideal
angles are traced back to the P–Ru–O angles of ca. 84Њ, which
arise from liberation of steric interaction between DMSO
ligands and the phosphorus ligand, and the formation of the
five-membered chelate rings. Other angles around the Ru atom
are near 90Њ. The Ru–O bond distances of 2.09 Å are similar to
those of other ruthenium complexes.7 The Ru–S(1) length of
2.250(2) Å and Ru–S(2) of 2.216(2) Å are slightly shorter than
those in 3b, suggesting that the trans influence of a Cl ligand is
higher than that of a O ligand. The S(2)–O(6) distance of
1.398(6) Å is shorter by 0.07 Å in comparison with those in 3b.
The Ru–Cl bond length in 4b is longer by 0.21 Å than the
average bond length of 3b, suggesting that phosphine has a
greater trans influence than the DMSO ligand. A similar trend
has been observed in DMSO complexes of platinum.23 The
O(2)–C(6) and O(4)–C(13) bond lengths are shorter by 0.07 Å
than those of the O(1)–C(2) and O(3)–C(9) lengths.
Fig. 3 An ORTEP diagram of complex 5a.
explained by the stereospecific addition of CO to a five-co-
ordinate intermediate formed by initial dissociation of one of
the ether oxygen atoms. The H NMR spectrum showed only
one singlet at δ 3.53 for methoxy groups, incompatible with the
structure in the solid state, due to rapid ligand exchange among
four methoxy groups.
1
The cations in complexes 3b or 4b are typical of those in
phosphonium salts. The geometry around the P(2) atom is
quasi-tetrahedral.
Complexes 5a and 6b. Selected bond lengths and angles are
listed in Table 3. The adjacent A–Ru–B bond angles of 5a and
5b fall in the range 90 3Њ, and the molecules adopt an octa-
hedral configuration. Three isocyanide ligands occupy the
meridional positions and two Cl atoms are in mutually trans
positions. The Ru–C bond length (1.966 Å) of isocyanide at the
trans position to the phosphine ligand is not significantly differ-
ent from other Ru–C bond lengths of ca. 2.000 Å. The Ru–C–N
and C–N–C bond angles in isocyanide ligands are near the ideal
values.
Crystal structures
Complexes 3b and 4b. Perspective drawings of complexes 3b
and 4b are illustrated in Figs. 1 and 2. Selected bond lengths
and angles are listed in Table 2. The molecules of 3b and
4b consist of the discrete salts; the anions are [RuCl3(DMSO-
S)3]Ϫ for 3b and [RuCl(DMSO-S)2{PPh(C6H3OMe-6-O-2)2-
P,O,OЈ)]Ϫ for 4b , and the cation has a common structural unit
[BDPMPP(CH2Cl)]ϩ.
The geometry of the anion of complex 3b has a facial octa-
hedral structure and the A–Ru–B angles between cis ligands fall
in the range 86–93Њ. The average Ru–Cl and Ru–S bond lengths
are 2.430 and 2.269 Å, respectively. These bond lengths were
in agreement with those in the anionic part of [NH2Me2]-
[RuCl3(DMSO)3].22
Complex 6. Selected bond lengths and angles are listed in
Table 4. Two P and two Cl atoms each occupy mutually
trans positions. The CO ligand is in a trans position to the
ether oxygen atom (Fig. 5). The Ru–O(4) bond length of
2.270 Å is longer by 0.03 Å than those found in 2.7b The
Ru–P(2) bond length (2.339 Å) in the chelated ligand is shorter
than non-chelated Ru–P(1) of 2.422 Å, resulting in different
The Ru atom in the anion of complex 4b is in a distorted
octahedral configuration and is surrounded by two DMSO
molecules, a Cl anion and a tridentate P,O,OЈ ligand derived
J. Chem. Soc., Dalton Trans., 1999, 4003–4008
4007

View Article Online
Table 4 Selected bond lengths (Å) and angles (Њ) of [RuCl2(MDMPP)-
(MDMPP-κ2P,O)(CO)] 6
Dunbar, A. Quillevere and S. C. Haefner, Acta Crystallogr., Sect. C,
1991, 47, 2319; K. R. Dunbar and L. E. Pence, Acta Crystallogr.,
Sect. C, 1991, 47, 23; S. C. Haefner, K. R. Dunbar and C. Bender,
J. Am. Chem. Soc., 1991, 113, 9540; S. C. Haefner and K. Dunbar,
Organometallics, 1992, 11, 1431; J. I. Dulebophn, S. C. Haefner,
K. R. Dunbar and K. A. Berglund, Chem. Mater., 1992, 4, 506;
K. R. Dunbar, Comments Inorg. Chem., 1992, 6, 313; K. R. Dunbar
and A. Quillevere, Polyhedron, 1993, 12, 807; Organometallics, 1993,
12, 618; K. R. Dunbar, J. H. Matonic and V. P. Saharan, Inorg.
Chem., 1994, 33, 25; K. R. Dunbar, S. C. Haefner, C. E. Uzelmeier
and A. Howard, Inorg. Chim. Acta, 1995, 240, 527; L.-J. Baker,
R. C. Bott, G. A. Bowmaker, P. C. Healy, B. W. Skelton, P. A.
Schwerdtfeger and A. H. White, J. Chem. Soc., Dalton Trans., 1995,
1341 and refs. therein.
Ru–Cl(1)
Ru–P(1)
Ru–O(4)
C(41)–O(1)
O(3)–C(38)
O(5)–C(6)
2.393(2)
2.422(2)
2.270(5)
1.142(9)
1.38(1)
Ru–Cl(2)
Ru–P(2)
Ru–C(41)
O(2)–C(34)
O(4)–C(2)
2.381(2)
2.339(2)
1.810(7)
1.363(9)
1.403(9)
1.339(9)
Cl(1)–Ru–Cl(2)
Cl(1)–Ru–P(2)
Cl(1)–Ru–C(41)
Cl(2)–Ru–P(2)
Cl(2)–Ru–C(41)
P(1)–Ru–O(4)
P(2)–Ru–O(4)
Ru–O(4)–C(2)
Ru–P(2)–C(1)
Ru–C(41)–O(1)
168.84(7)
85.28(7)
97.3(3)
93.59(7)
93.8(3)
101.8(1)
78.3(1)
117.3(4)
102.4(2)
175.9(2)
Cl(1)–Ru–P(1)
Cl(1)–Ru–O(4)
Cl(2)–Ru–P(1)
Cl(2)–Ru–O(4)
P(1)–Ru–P(2)
P(1)–Ru–C(41)
P(2)–Ru–C(41)
O(4)–C(2)–C(1)
P(2)–C(1)–C(2)
91.18(7)
84.5(2)
89.97(7)
87.4(3)
176.44(8)
89.0(2)
91.0(2)
5 (a) K. R. Dunbar and J.-S. Sun, J. Chem. Soc., Chem. Commun.,
1994, 2387; (b) J.-S. Sun, C. E. Uzelmeier D. L. Ward and K. R.
Dunbar, Polyhedron, 1998, 11/12, 2049.
6 K. R. Dunbar, J.-S. Sun and A. Quillevéré, Inorg. Chem., 1994, 33,
3598.
118.0(2)
117.8(6)
7 (a) Y. Yamamoto, R. Sato, M. Ohshima, F. Matsuo and C. Sudoh,
J. Organomet. Chem., 1995, 489, C68; Y. Yamamoto, R. Sato,
F. Matsuo, C. Sudoh and T. Igoshi, Inorg. Chem., 1996, 35, 2329.
8 X.-H. Han and Y. Yamamoto, J. Organomet. Chem., 1998, 561, 157.
9 W. L. Reynolds, Prog. Inorg. Chem., 1970, 12, 1.
10 T. Tanase and S. J. Lippard, Inorg. Chem., 1995, 34, 4682.
11 T. Tanase, T. Aiko and Y. Yamamoto, Chem. Commun., 1996, 2341.
12 I. P. Evans, A. Spencer and G. Wilkinson, J. Chem. Soc., Dalton
Trans., 1973, 206; (b) E. Alessio, G. Balducci, M. Calligaris,
G. Costa, W. M. Attia and G. Mestroni, Inorg. Chem., 1991, 30, 609.
13 H. H. Walborsky and G. E. Niznik, J. Org. Chem., 1972, 37, 187.
14 D. T. Cromer and J. T. Waber, International Tables for X-Ray
Crystallography, Kynoch Press, Birmingham, 1974, Table 2.2A.
15 J. A. Ibers and W. C. Hamilton, Acta Crystallogr., 1964, 17, 781.
16 D. C. Creagh and W. J. McAuley, International Tables for X-Ray
Crystallography, Kluwer, Boston, 1992, vol. C, Table 4.2.6.8,
pp. 200–206.
co-ordination modes, and is longer by 0.1 Å than the corre-
sponding bond lengths in 2,7b due to the greater trans influence
of the phosphorus ligand than the ether O.
Acknowledgements
We thank Professor Shigetoshi Takahashi and Ms Fumie Takei
in The Institute of Industrial and Scientific Research, Osaka
University for measurements of FAB mass spectra. One of the
authors (J.-F. M.) acknowledges the 60th Aniversary Found-
ation of Toho University.
17 TEXSAN, Crystal Structure Analysis Package, Molecular Structure
Corporation, Houston, TX, 1985 and 1992.
18 P. T. Beurskens, G. Admiraal, G. Beurskens, W. P. Bosman, S.
Garcia-Granda, R. O. Gould, J. M. M. Smits and C. Smykalla,
DIRDIF 92, Technical Report of the Crystallographic Laboratory,
University of Nijmegen, 1992.
19 K. R. Dunbar and A. Quillevéré, Angew. Chem., Int. Ed. Engl.,
1993, 32, 293.
20 M. Wada, Synth. Org. Chem., 1986, 44, 957.
21 C. K. Johnson, ORTEP II, Report ORNL-5138, Oak Ridge
National Laboratory, Oak Ridge, TN, 1976.
22 R. S. McMillan, A. Mercer, B. R. James and J. Trotter, J. Chem.
Soc., Dalton Trans., 1975, 1006.
23 P. Kapoor, K. Luvquist and A. Oskarsson, J. Mol. Struct., 1998,
470, 39.
References
1 (a) M. Wada and S. Higashimura, J. Chem. Soc., Chem. Commun.,
1984, 482; M. Wada, S. Higashimura and A. Tsuboi, J. Chem. Res.,
1985, (S) 38, (M) 467.
2 M. Wada and A. Tsuboi, J. Chem. Soc., Perkin Trans. 1, 1987, 151.
3 M. Wada, A. Tsuboi, K. Nishimura and T. Erabi, Nippon Kagaku
Kaishi, 1987, 1284; H. Kurosawa, A. Tsuboi, Y. Kawasaki and M.
Wada, Bull. Chem. Soc. Jpn., 1987, 60, 3563.
4 K. R. Dunbar, S. C. Haefner and L. E. Pence, J. Am. Chem. Soc.,
1989, 111, 5504; K. R. Dunbar, S. C. Haefner and D. J. Burzynski,
Organometallics, 1990, 9, 1347; S.-J. Chen and K. R. Dunbar, Inorg.
Chem., 1990, 29, 588; K. R. Dunbar, S. C. Haefner and A.
Quillevere, Polyhedron, 1990, 9, 1695; K. R. Dunbar, S. C. Haefner
and P. M. Swepston, J. Chem. Soc., Chem. Commun., 1991, 460;
S.-J. Chen and K. R. Dunbar, Inorg. Chem., 1990, 29, 2018; K. R.
Paper 9/06435D
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J. Chem. Soc., Dalton Trans., 1999, 4003–4008