Cyanide-bridged linkage isomers with catecholateruthenium(ii) centres bound to Mn(i) or M(alkyne) units

Article abstract of DOI:10.1039/b700549k

Two series of stable cyanide-bridged linkage isomers, namely [(o-O ₂C₆Cl₄)(Ph₃P)(OC) ₂Ru(-XY)MnL(NO)(η-C₅Me₅)] (XY = CN or NC, L = CNBu^t or CNXyl) and [(o-O₂C₆Cl ₄)L(OC)₂Ru(-XY)M(CO)(PhCCPh)Tp′] {M = Mo or W, L = PPh₃ or P(OPh)₃, Tp′ = hydrotris(3,5- dimethylpyrazolyl)borate} have been synthesised; pairs of isomers are distinguishable by IR spectroscopy and cyclic voltammetry. The molecular structure of [(o-O₂C₆Cl₄)(Ph ₃P)(OC)₂Ru(-NC)Mo(CO)(PhCCPh)Tp′] has the catecholate-bound ruthenium atom cyanide-bridged to a Mo(CO)(PhCCPh)Tp′ unit in which the alkyne acts as a four-electron donor; the alignment of the alkyne relative to the Mo-CO vector suggests the fragment (CN)Ru(CO) ₂(PPh₃)(o-O₂C₆Cl₄) acts as a π-acceptor ligand. The complexes [(o-O₂C₆Cl ₄)(Ph₃P)(OC)₂Ru(-XY)Mn(NO)L(η-C ₅Me₅)] undergo three sequential one-electron oxidation processes with the first and third assigned to oxidation of the ruthenium-bound o-O₂C₆Cl₄ ligand; the second corresponds to oxidation of Mn(i) to Mn(ii). The complexes [(o-O₂C ₆Cl₄)L(OC)₂Ru(-XY)M(CO)(PhCCPh)Tp′] are also first oxidised at the catecholate ligand; the second oxidation, and one-electron reduction, are based on the M(CO)(PhCCPh)Tp′ fragment. Chemical oxidation of [(o-O₂C₆Cl₄)(Ph ₃P)(OC)₂Ru(-XY)MnL(NO)(η-C₅Me₅)] with [Fe(η-C₅H₄COMe)(η-C₅H ₅)][BF₄], or of [(o-O₂C₆Cl ₄)L(OC)₂Ru(-XY)M(CO)(PhCCPh)Tp′] with AgBF ₄, gave the paramagnetic monocations [(o-O₂C ₆Cl₄)(Ph₃P)(OC)₂Ru(-XY)MnL(NO) (η-C₅Me₅)]⁺ and [(o-O₂C ₆Cl₄)L(OC)₂Ru(-XY)M(CO)(PhCCPh)Tp′] ⁺, the ESR spectra of which are consistent with ruthenium-bound semiquinone ligands. Linkage isomers are distinguishable by the magnitude of the ³¹P hyperfine coupling constant; complexes with N-bound Ru(o-O ₂C₆Cl₄) units also show small hyperfine coupling to the nitrogen atom of the cyanide bridge. The Royal Society of Chemistry 2007.

Full text of DOI:10.1039/b700549k

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www.rsc.org/dalton | Dalton Transactions
Cyanide-bridged linkage isomers with catecholateruthenium(II) centres bound
to Mn(I) or M(alkyne) units
Christopher J. Adams, Neil G. Connelly* and Sriwipha Onganusorn
Received 12th January 2007, Accepted 28th February 2007
First published as an Advance Article on the web 19th March 2007
DOI: 10.1039/b700549k
Two series of stable cyanide-bridged linkage isomers, namely [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-XY)MnL-
(NO)(g-C5Me5)] (XY = CN or NC, L = CNBut or CNXyl) and [(o-O2C6Cl4)L(OC)2Ru(l-XY)M(CO)-
(PhC≡CPh)Tpꢀ] {M = Mo or W, L = PPh3 or P(OPh)3, Tpꢀ = hydrotris(3,5-dimethylpyrazolyl)borate}
have been synthesised; pairs of isomers are distinguishable by IR spectroscopy and cyclic voltammetry.
The molecular structure of [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)Mo(CO)(PhC≡CPh)Tpꢀ] has the
catecholate-bound ruthenium atom cyanide-bridged to a Mo(CO)(PhC≡CPh)Tpꢀ unit in which the
alkyne acts as a four-electron donor; the alignment of the alkyne relative to the Mo–CO vector suggests
the fragment (CN)Ru(CO)2(PPh3)(o-O2C6Cl4) acts as a p-acceptor ligand. The complexes [(o-O2C6Cl4)-
(Ph3P)(OC)2Ru(l-XY)Mn(NO)L(g-C5Me5)] undergo three sequential one-electron oxidation processes
with the first and third assigned to oxidation of the ruthenium-bound o-O2C6Cl4 ligand; the second
corresponds to oxidation of Mn(I) to Mn(II). The complexes [(o-O2C6Cl4)L(OC)2Ru(l-XY)M(CO)-
(PhC≡CPh)Tpꢀ] are also first oxidised at the catecholate ligand; the second oxidation, and one-electron
reduction, are based on the M(CO)(PhC≡CPh)Tpꢀ fragment. Chemical oxidation of [(o-O2C6Cl4)-
(Ph3P)(OC)2Ru(l-XY)MnL(NO)(g-C5Me5)] with [Fe(g-C5H4COMe)(g-C5H5)][BF4], or of
[(o-O2C6Cl4)L(OC)2Ru(l-XY)M(CO)(PhC≡CPh)Tpꢀ] with AgBF4, gave the paramagnetic
monocations [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-XY)MnL(NO)(g-C5Me5)]+ and [(o-O2C6Cl4)L(OC)2Ru-
(l-XY)M(CO)(PhC≡CPh)Tpꢀ]+, the ESR spectra of which are consistent with ruthenium-bound
semiquinone ligands. Linkage isomers are distinguishable by the magnitude of the 31P hyperfine
coupling constant; complexes with N-bound Ru(o-O2C6Cl4) units also show small hyperfine coupling to
the nitrogen atom of the cyanide bridge.
Introduction
Results and discussion
As an extension of previous studies, by us1 and others,2 of
complexes in which a cyanide ligand bridges two metal-based
redox centres, we have recently reported3 a series of homobinuclear
species, [(o-O2C6Cl4)L(OC)2Ru(l-CN)Ru(CO)2Lꢀ(o-O2C6Cl4)]−
{L or Lꢀ = PPh3 or P(OPh)3}, in which sequential one-electron
oxidation occurs at the two ligand-based (catecholate) centres. We
now describe heterobinuclear species in which the ligand-based
redox centres Ru(XY)(CO)2L(o-O2C6Cl4) {XY = CN or NC, L =
PPh3 or P(OPh)3} are C- or N-bound either to a redox-active Mn(I)
centre, as in [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-XY)MnL(NO)(g-
C5Me5)] (XY = CN or NC, L = CNBut or CNXyl), related
to previous species such as [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-
NC)Mn(CO)2(PEt3)(dppe)-cis],4 or to an M(alkyne) group, as in
[(o-O2C6Cl4)L(OC)2Ru(l-XY)M(CO)(PhC≡CPh)Tpꢀ] (M = Mo
or W), where redox activity is centred on the metal–alkyne unit. In
both series, electrochemical and spectroscopic studies have shed
light on the effect of linkage isomerisation and ancillary ligand
sets on electron transfer between linked metal- and ligand-based
redox centres.
The synthesis and characterisation of [(o-O2C6Cl4)(Ph3P)(OC)2-
Ru(l-XY)MnL(NO)(g-C5Me5)] (XY = CN or NC, L = CNBut or
CNXyl) and [(o-O2C6Cl4)L(OC)2Ru(l-XY)M(CO)(PhC≡CPh)-
Tpꢀ] {XY = CN or NC, M = Mo or W, L = PPh3 or P(OPh)3}
The complexes [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-CN)MnL(NO)(g-
C5Me5)] (L = CNBut 1 or CNXyl 2) were prepared by the halide
replacement reaction of [MnIL(NO)(g-C5Me5)] with [NEt4][Ru-
(CN)(PPh3)(CO)2(o-O2C6Cl4)], and the linkage isomers [(o-O2C6-
Cl4)(Ph3P)(OC)2Ru(l-NC)MnL(NO)(g-C5Me5)] (L = CNBut 3 or
CNXyl 4) by the bridge-splitting reactions of [{Ru(CO)2(PPh3)(l-
o-O2C6Cl4)}2] with [Mn(CN)L(NO)(g-C5Me5)].
Similarly, [(o-O2C6Cl4)L(OC)2Ru(l-CN)M(CO)(PhC≡CPh)-
Tpꢀ] {M = Mo, L = PPh3 5 or P(OPh)3 6; M = W, L = PPh3 7 or
P(OPh)3 8} were synthesised by the carbonyl substitution reactions
of [M(CO)2(PhC≡CPh)Tpꢀ][BF4] with [NEt4][Ru(CN)(CO)2L(o-
O2C6Cl4)], and their linkage isomers, [(o-O2C6Cl4)L(OC)2Ru(l-
NC)M(CO)(PhC≡CPh)Tpꢀ] {M = Mo, L = PPh3 9 or P(OPh)3
10; M = W, L = PPh3 11 or P(OPh)3 12}, by the bridge cleavage
reactions of [{Ru(CO)2L(l-o-O2C6Cl4)}2] with [M(CN)(CO)-
(PhC≡CPh)Tpꢀ].
All of the complexes 1–12 (Scheme 1) were characterised by
elemental analysis, IR spectroscopy and cyclic voltammetry, and
[(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)Mo(CO)(PhC≡CPh)Tpꢀ] 9 by
School of Chemistry, University of Bristol, Bristol, UK BS8 1TS. E-mail:
neil.connelly@bristol.ac.uk; Fax: 0117 929 0509; Tel: 0117 928 8162
1904 | Dalton Trans., 2007, 1904–1910
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Table 1 Analytical and IR spectroscopic data for [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-XY)MnL(NO)(g-C5Me5)]z
Analysis (%)b
C
IR/cm−1c
Complexa
z
XY
L
Colour
Yield (%)
H
N
m(CNR) m(CN)
m(CO)
m(NO)
d
1
0
0
0
0
CN
CN
NC
NC
CNBut
CNXyl
CNBut
CNXyl
CNBut
CNXyl
CNBut
CNXyl
Yellow
Yellow
Orange
Orange
Red-purple 31
Red-purple 62
Red-purple 83
Red-purple 65
46
32
34
64
50.8 (50.7) 4.5 (4.0)
52.9 (53.0) 4.1 (3.8)
50.4 (50.7) 3.9 (4.0)
52.8 (53.0) 4.1 (3.8)
46.5 (46.7) 3.8 (3.7)
49.4 (48.9) 3.8 (3.5)
47.1 (46.7) 3.8 (3.7)
49.4 (48.9) 3.8 (3.5)
3.8 (4.2) 2164m
3.9 (4.0) 2129m
3.5 (4.2) 2160m
4.0 (3.7) 2123m
3.6 (3.9) 2166m
3.4 (3.7) 2135m
3.4 (3.9) 2163m
3.1 (3.7) 2122m
2049, 1986 1734m
2048, 1984 1740m
2050, 1984 1740ms
d
2
3
2139m
4
2145mw 2049, 1984 1746ms
d
1+
2+
3+
4+
1+ CN
1+ CN
1+ NC
1+ NC
2081, 2030 1744ms
2081, 2029 1749m
2082, 2028 1749m
2082, 2029 1753m
d
2129m
2140m
a Cations isolated as [BF4]− salts. b Calculated values in parentheses. c Strong (s) absorptions in CH2Cl2 unless otherwise stated; w = weak, m = medium.
d Coincident with m(CNR).
from those of [Mn(CN)L(NO)(g-C5Me5)] {L = CNBut, m(CN) =
X-ray crystallography (see below). Analytical data for 1–4 and
2101 cm−1;5 L = CNXyl, m(CN) = 2102 cm−1},6 with 5–8
5–12 are given in Tables 1 and 2 respectively.
shifted by 13–19 cm−1 from those of [Ru(CN)(CO)2L(o-O2C6Cl4)]−
{L = PPh3, m(CN) = 2127 cm−1; L = P(OPh)3, m(CN) =
2132 cm−1},3 and with 9–12 shifted by ca. 35 cm−1 from those
of [M(CN)(CO)(PhC≡CPh)Tpꢀ] {M = Mo or W, m(CN) =
2108 cm−1}.6
The effect of cyanide bridge orientation on the two sets of
linkage isomers is small but significant. Thus, m(NO) in 1 and
2, and m(CO) in 5–8, with an Ru(l-CN)Mn or Ru(l-CN)M
linkage, are lower in energy (by ca. 10–15 cm−1) than in 3 and
4 and in 9–12, with an Ru(l-NC)Mn or Ru(l-NC)M skeleton, i.e.
(NC)Ru(CO)2(PPh3)(o-O2C6Cl4) acts as a better net donor than
(CN)Ru(CO)2(PPh3)(o-O2C6Cl4). In addition, m(CN) is lower in
energy (by 1–6 cm−1) for 5–8 (Mo or W N-bound to cyanide) than
for 9–12 (Mo or W C-bound to cyanide).
The structure of [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)-
Mo(CO)(PhC≡CPh)Tpꢀ]
The structure of 9, determined as a representative example of
the alkyne complexes 5–12, (suitable crystals of 1–4 could not be
grown) is shown in Fig. 1 with selected bond lengths and angles
given in Table 3. The ruthenium atom is linked to molybdenum
by a slightly bent cyanide bridge [C(30)–N(7)–Ru(1) = 176.9(5),
N(7)–C(30)–Mo(1) = 174.3(5)◦]. Both Ru and Mo centres are
approximately octahedral, e.g. C(31)–Ru(1)–O(3) = 92.8(2)◦ and
C(39)–Mo(1)–C(30) = 87.4(2)◦, with Ru bound to two cis CO lig-
ands, PPh3 and a chelating o-O2C6Cl4 ligand and Mo coordinated
to CO, tridentate Tpꢀ and PhC≡CPh.
Scheme 1 Complexes 1–12
The IR spectra of 1–12 show two bands for the Ru(CO)2L(o-
O2C6Cl4) group, the energies of which are only significantly
affected by the nature of L {i.e. P(OPh)3 complexes show m(CO)
bands at ca. 20 cm−1 higher energy than PPh3 analogues}. The
energies of m(CNR) and m(NO) for the Mn(CNR)(NO)(g-C5Me5)
group of 1–4, and of m(CO) for the M(CO)(PhC≡CPh)Tpꢀ group
of 5–12, are essentially unaffected by varying L in Ru(CO)2L(o-
O2C6Cl4) {although m(CNBut) in the former is significantly higher
than m(CNXyl) (by ca. 35 cm−1), and m(CO) in the latter is higher
in energy by 20–30 cm−1 for the molybdenum complexes than the
tungsten analogues}.
The C–C distances in the o-O2C6Cl4 ligand are close to
˚
1.40 A and the C–O distances in the Ru-chelate ring {C(33)–
˚
O(3) = 1.314(5), C(34)–O(4) = 1.332(6) A} are similar to those
˚
of [NEt4][Ru(CN)(CO)2(PPh3)(o-O2C6Cl4)] {1.314(4)–1.336(4) A}
and [NBu4][(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-CN)Ru(CO)2(PPh3)(o-
3
˚
O2C6Cl4)] {1.324(4)–1.328(4) A}. The structural data are there-
fore consistent with the o-O2C6Cl4 ligand acting as a catecholate.
The Mo–alkyne bond lengths [Mo(1)–C(22) = 2.022(5), Mo(1)–
˚
C(23) = 2.059(5) A] are characteristic of a four-electron donating
alkyne7 and the angle between the C≡C and Mo–C(O) vectors, b,
is 21.8◦. Better donors, L, in [M(CO)L(PhC≡CPh)Tpꢀ]z (M = Mo
or W) lead to closer alignment of the alkyne with the CO ligand
(i.e. to a smaller b8) {e.g. compare [Mo(CO)2(PhC≡CPh)Tpꢀ]+
(b = 22.8◦)9 with [WX(CO)(MeC≡CMe)Tpꢀ] (X = Cl, b = 7.9;
The bridging cyanide bands for 1–12 occur at higher energy,
and with increased intensity, than the terminal cyanide bands
of the mononuclear precursors, with 3–4 shifted by 40–45 cm−1
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Table 2 Analytical and IR spectroscopic data for [(o-O2C6Cl4)L(OC)2Ru(l-XY)M(CO)(PhC≡CPh)Tpꢀ]z
Analysis (%)b
IR/cm−1c
Complexa
z
L
XY
M
Colour
Yield (%)
C
H
N
m(CN)
m(CO)Mo,W
m(CO)Ru
5
6
0
0
0
0
0
0
0
0
1+
1+
1+
1+
1+
1+
1+
1+
PPh3
P(OPh)3
PPh3
P(OPh)3
PPh3
P(OPh)3
PPh3
P(OPh)3
PPh3
P(OPh)3
PPh3
P(OPh)3
PPh3
P(OPh)3
PPh3
CN
CN
CN
CN
NC
NC
NC
NC
CN
CN
CN
CN
NC
NC
NC
NC
Mo
Mo
W
Green
Green
Green
Green
Yellow
Yellow
Green
Green
Red-purple
Red-purple
Red-purple
Red-purple
Red-purple
Red-purple
Red-purple
Red-purple
54
30
40
34
66
82
85
45
44
74
49
37
84
90
58
67
53.4 (53.0)
51.4 (51.1)
49.3 (49.7)
46.3 (46.1)
52.9 (53.0)
51.1 (51.1)
49.9 (49.7)
48.3 (48.0)
48.8 (48.6)
47.7 (48.0)
44.0 (44.1)
45.6 (45.2)
49.4 (49.7)
48.0 (48.0)
46.5 (46.7)
45.6 (45.2)
3.9 (3.7)
3.5 (3.5)
3.6 (3.4)
3.3 (3.3)
3.8 (3.7)
3.4 (3.5)
3.4 (3.4)
3.3 (3.3)
3.0 (3.4)
3.5 (3.3)
3.3 (3.2)
3.1 (3.2)
3.4 (3.4)
3.4 (3.3)
3.1 (3.2)
3.6 (3.2)
7.2 (7.6)
7.2 (7.3)
6.8 (7.1)
6.7 (6.5)
7.3 (7.6)
7.1 (7.3)
7.2 (7.1)
6.6 (6.9)
6.6 (6.9)
6.6 (6.9)
6.5 (6.2)
6.5 (6.5)
6.8 (7.1)
7.0 (6.9)
6.4 (6.7)
6.2 (6.5)
2146
2151
2142
2145
2143
2145
2141
2142
2154
2159
2147
2152
2137
2136
2133
2132
1955m
1955m
1930m
1930m
1961m
1962m
1939m
1940m
1959
1960
1935
1936
1965
2049, 1988
2065, 2007
2049, 1989
2067, 2010
2050, 1985
2067, 2008
2050, 1985
2069, 2008
2082, 2032
2098, 2050
2082, 2033
2098, 2051
2082, 2029
2100, 2050
2082, 2029
2101, 2051
7
8d
9
W
Mo
Mo
W
10
11
12
5+d
6+
W
Mo
Mo
W
7+e
8+
W
9+
Mo
Mo
W
10+
11+
12+
1966
1945
1946
P(OPh)3
W
a Cations isolated as [BF4]− salts. b Calculated values in parentheses. c Strong absorptions in CH2Cl2 unless otherwise stated; m = medium. d Calculated
as a 2 : 1 CH2Cl2 : solvate. e Calculated as a 2 : 3 CH2Cl2 : solvate.
◦
˚
Table 3 Selected bond lengths (A) and angles ( ) for [(o-O2C6Cl4)(Ph3P)-
(OC)2Ru(l-NC)Mo(CO)(PhC≡CPh)Tpꢀ] 9
C(30)–N(7)
Mo(1)–C(39)
Mo(1)–C(22)
Mo(1)–C(23)
Mo(1)–C(30)
Mo(1)–N(4)
Mo(1)–N(2)
Mo(1)–N(6)
Ru(1)–N(7)
Ru(1)–C(31)
Ru(1)–C(32)
Ru(1)–O(3)
Ru(1)–O(4)
Ru(1)–P(1)
C(33)–O(3)
C(34)–O(4)
C(22)–C(23)
C(31)–O(1)
C(32)–O(2)
C(39)–O(5)
C(33)–C(34)
C(34)–C(35)
C(35)–C(36)
C(36)–C(37)
C(37)–C(38)
C(38)–C(33)
1.148(6)
1.984(6)
2.022(5)
2.059(5)
2.147(6)
2.194(4)
2.220(4)
2.242(4)
2.098(5)
1.884(6)
1.894(6)
2.054(3)
2.064(3)
2.342(2)
1.314(5)
1.332(6)
1.308(7)
1.135(6)
1.132(6)
1.150(6)
1.415(7)
1.405(7)
1.404(7)
1.375(7)
1.392(7)
1.398(7)
C(39)–Mo(1)–C(22)
C(39)–Mo(1)–C(23)
C(22)–Mo(1)–C(23)
C(39)–Mo(1)–C(30)
C(22)–Mo(1)–C(30)
C(23)–Mo(1)–C(30)
N(7)–C(30)–Mo(1)
C(30)–N(7)–Ru(1)
C(31)–Ru(1)–C(32)
C(31)–Ru(1)–O(3)
C(32)–Ru(1)–O(3)
C(31)–Ru(1)–O(4)
C(32)–Ru(1)–O(4)
O(3)–Ru(1)–O(4)
C(31)–Ru(1)–N(7)
C(32)–Ru(1)–N(7)
N(7)–Ru(1)–P(1)
ba
107.6(2)
72.6(2)
37.5(2)
87.4(2)
101.6(2)
87.0(2)
174.3(5)
176.9(5)
91.7(3)
92.8(2)
175.0(2)
173.5(2)
94.1(2)
81.2(2)
90.5(2)
92.9(2)
174.0(1)
21.8
Fig. 1 The molecular structure of [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)-
Mo(CO)(PhC≡CPh)Tpꢀ] 9. Hydrogen atoms have been omitted for clarity.
X = Br, b = 6.8◦ }. On this basis, therefore, the C-bound fragment
10
a b = the angle between the C≡C and Mo–C(O) vectors.
(CN)Ru(CO)2(PPh3)(o-O2C6Cl4) appears to act as a p-acceptor
ligand, i.e like a metallaisocyanide.
quinone complexes of Ru(II); the potential of the second wave
depends on the ligands on the manganese centre and therefore
corresponds to oxidation of Mn(I) to Mn(II). The potential of
the second oxidation, but not the others, also depends on the
orientation of the cyanide bridge with that for 1 and 2 (0.93 and
1.03 V respectively) 160 mV more negative than for their respective
linkage isomers 3 and 4.
The CVs of [(o-O2C6Cl4)L(OC)2Ru(l-XY)M(CO)(PhC≡CPh)-
Tpꢀ] {XY = CN or NC, M = Mo or W, L = PPh3 or P(OPh)3}
5–12 (Table 5) show one reduction wave and two reversible
oxidation waves. Unlike for 5–10, the reduction waves of 11
Cyclic voltammetric studies
The cyclic voltammograms (CVs) of [(o-O2C6Cl4)(Ph3P)(OC)2-
Ru(l-XY)Mn(NO)L(g-C5Me5)] (XY = CN or NC, L = CNBut or
CNXyl)} 1–4 show three sequential one-electron oxidation waves
in the potential range 0.0 to 1.8 V (Table 4). The potentials of the
first and third waves are similar to those found for the first and
second oxidations of [Ru(CO)2(PPh3)2(o-O2C6Cl4)] {0.59 and 1.62
11
V} and [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)Mn(PPh3)(NO)(g-
4
C5H4Me)] {0.58 and 1.68(I) V} and are thus assigned to oxidation
at the ruthenium-bound o-O2C6Cl4 ligand, i.e. to semiquinone and
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Table 4 Electrochemical data for the oxidation of [(o-O2C6Cl4)(Ph3P)-
(OC)2Ru(l-XY)MnL(NO)(g-C5Me5)]
analogue. The first oxidation site is therefore the catecholate
ligand bound to ruthenium. The potential of the second wave
does depend on M, with tungsten complexes more easily oxidised
by ca. 100 mV. It is also affected by the orientation of the cyanide
bridge, as are the IR spectroscopic data. Thus, for example, both
m(CO) and Eo are less for 5 than for the linkage isomer 9 (i.e.
linkage isomers are distinguishable by IR spectroscopy and cyclic
voltammetry).
Potential/Va
Complex
XY
L
E◦ (Ru)
ꢀ
E◦ (Mn)
ꢀ
ꢀ
1
2
3
4
CN
CN
NC
NC
CNBut
CNXyl
CNBut
CNXyl
0.53, 1.55(I)
0.55, 1.59(I)
0.56, 1.63(I)
0.57, 1.63(I)
0.93
1.03
1.09
1.19
◦
a Potentials calibrated vs. [Fe(g-C5H4COMe)(g-C5H5)] (at 0.74 V). E for
ꢀ
reversible wave unless stated otherwise. For an irreversible (I) process, the
Chemical oxidation of [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-XY)-
MnL(NO)(g-C5Me5)] (XY = CN or NC, L = CNBut or CNXyl)
and [(o-O2C6Cl4)L(OC)2Ru(l-XY)M(CO)(PhC≡CPh)Tpꢀ]
{XY = CN or NC, M = Mo or W, L = PPh3 or P(OPh)3}
oxidation peak potential, (Ep)ox, is given at a scan rate of 200 mV s−1
.
Table 5 Electrochemical data for [(o-O2C6Cl4)L(OC)2Ru(l-XY)M(CO)-
(PhC≡CPh)Tpꢀ]
In accord with the potentials of their first oxidation waves, treat-
ment of [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-XY)MnL(NO)(g-C5Me5)]
(XY = CN or NC, L = CNBut or CNXyl) with one
equivalent of [Fe(g-C5H4COMe)(g-C5H5)][BF4] in CH2Cl2 gave
purple solutions which were filtered, reduced to low volume
and then treated with n-hexane to give the one-electron oxi-
dation products [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-CN)MnL(NO)(g-
C5Me5)][BF4] (L = CNBut 1+[BF4]− or CNXyl 2+[BF4]−) and [(o-
O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)MnL(NO)(g-C5Me5)][BF4] (L =
CNBut 3+[BF4]− or CNXyl 4+[BF4]−). Similar treatment of [(o-
O2C6Cl4)L(OC)2Ru(l-XY)M(CO)(PhC≡CPh)Tpꢀ] {XY = CN
or NC, M = Mo or W, L = PPh3 or P(OPh)3} with one
equivalent of AgBF4 gave the salts [(o-O2C6Cl4)L(OC)2Ru(l-
CN)M(CO)(PhC≡CPh)Tpꢀ][BF4] {M = Mo, L = PPh3 5+[BF4]−
Potential/Va
ꢀ
Complex
L
XY
M
E◦ (Ru) E◦ (M)
ꢀ
5
6
PPh3
CN Mo 0.54
P(OPh)3 CN Mo 0.63
1.05
1.06
0.90
0.95
1.12
1.14
1.02
1.05
−1.09
−1.08
7
PPh3
P(OPh)3 CN
PPh3
P(OPh)3 NC Mo 0.64
CN
W
W
0.53
−1.49
8
0.62
−1.49
9
NC Mo 0.56
−1.07
10
11
12
−1.05
PPh3
P(OPh)3 NC
NC
W
W
0.56
0.65
−1.44(I), −1.52b
−1.45(I), −1.52b
◦
ꢀ
a Potentials calibrated vs. [Fe(g-C5Me5)2] (at −0.08 V). E for reversible
wave unless stated otherwise. For an irreversible (I) process, the reduction
peak potential, (Ep)red, is given at a scan rate of 200 mV s−1 b The
.
irreversible reduction wave is followed by a reversible product wave (see
text).
or P(OPh)3 6+[BF4]−;
M
=
W,
L
=
PPh3 7+[BF4]− or
P(OPh)3 8+[BF4]−} and their isomers [(o-O2C6Cl4)L(OC)2Ru(l-
NC)M(CO)(PhC≡CPh)Tpꢀ][BF4] {M = Mo, L = PPh3 9+[BF4]−
or P(OPh)3 10+[BF4]−; M = W, L = PPh3 11+[BF4]− or P(OPh)3
12+[BF4]−}.
and 12 are irreversible and accompanied by a reversible product
wave at a more negative potential, −1.52 V, which corresponds
exactly with the reduction wave of the monomeric precursor,
[W(CN)(CO)(PhC≡CPh)Tpꢀ].6 In other words, one-electron re-
duction of the tungsten complexes 11 and 12 is followed by rapid
Ru–N bond cleavage whereas this bond in the molybdenum anions
9− and 10−, and the Ru(l-CN)M bridge in 5−–8−, is more robust.
Where the reduction wave is reversible, as in 5–10, the molybdenum
complexes are more easily reduced, by ca. 400 mV, than the
tungsten analogues, confirming the M(CO)(PhC≡CPh)Tpꢀ unit
to be the reduction site. Likewise, the tungsten centre is more
easily oxidised (at the second step) by ca. 100 mV.
All of the compounds 1+[BF4]−–12+[BF4]− were characterised
by elemental analysis and IR spectroscopy (data for 1+–4+ and 5+–
12+ are given in Tables 1 and 2 respectively), by cyclic voltammetry
(which showed waves at potentials effectively identical to those of
1–12 but with the first oxidation wave of the neutral complexes
now a reduction wave for the cations) and, for 2+, 4+–6+, 9+ and
10+, by ESR spectroscopy (Table 6).
The cations 1+–12+ each show the two carbonyl bands of the
Ru(CO)2 group shifted to higher wavenumber with respect to those
of the corresponding neutral complexes 1–12, by ca. 30–45 cm−1.
This shift, and the small increases in m(NO) (ca. 10 cm−1) and
m(CNR) (1–6 cm−1) for 1–4 and in m(CO) (ca. 5–10 cm−1) for the
Like 1–4, the first oxidation potential of 5–12 is independent
of M and the orientation of the cyanide bridge although it is
ca. 100 mV more negative for a PPh3 complex than a P(OPh)3
Table 6 ESR spectroscopic data for heterobinuclear semiquinone complexes of ruthenium(II).
A/G
Complex
giso
31P
99,101Ru
14N
35,37Cla
[(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-CN)Mn(CNXyl)(NO)(g-C5Me5)]+ 2+
[(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)Mn(CNXyl)(NO)(g-C5Me5)]+ 4+
[(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-CN)Mo(CO)(PhC≡CPh)Tpꢀ]+ 5+
[(o-O2C6Cl4){(PhO)3P}(OC)2Ru(l-CN)Mo(CO)(PhC≡CPh)Tpꢀ]+ 6+
[(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)Mo(CO)(PhC≡CPh)Tpꢀ]+ 9+
[(o-O2C6Cl4){(PhO)3P}(OC)2Ru(l-NC)Mo(CO)(PhC≡CPh)Tpꢀ]+ 10+
2.0020
2.0029
2.0020
2.0031
2.0032
2.0036
17.6
8.7
16.6
21.7
8.7
3.2
2.0
3.0
2.6
2.0
2.0
—
2.2
—
—
2.2
1.5
0.60
0.65
0.59
0.60
0.55
0.65
11.2
a Coupling to two chlorine atoms.
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M(CO) group (M = Mo or W) of 5–12 confirm oxidation of the
ruthenium-bound catecholate ligand to a semiquinone.
31P hyperfine coupling in the P(OPh)3 complexes 6+ and 10+ (21.7
and 11.2 G respectively) is greater than in the PPh3 analogues
5+ and 9+ though the approximate halving of A(31P) from C- to
N-binding of the cyanide bridge to ruthenium is again observed.
Though formally Ru(II) in both linkage isomers, e.g. in
[(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-CN)Mn(CNXyl)(NO)(g-C5Me5)]+
2+ and [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)Mn(CNXyl)(NO)(g-
C5Me5)]+ 4+, the positive charge on the N-bound ruthenium (i.e.
4+ in this case) leads to a contraction of the metal orbitals, poorer
overlap with the phosphorus atom, and hence a smaller value of
A(31P).
The lower energy (by ca. 5–10 cm−1) of the bridging cyanide
bands of 3+, 4+ and 8+–12+ relative to those of the corresponding
neutral complexes is in agreement with oxidation at the N-bound
Ru(o-O2C6Cl4) fragment. Similar behaviour is observed on oxida-
tion of [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)Mn(CO)2(PEt3)(dppe)-
cis],4 [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)Re(CO)3(o-phen)],12 [(g-
C5H4Me)(ON)(Ph3P)Mn(l-CN)Mn(CNXyl)(NO)(g-C5H4Me)]+,5
[(OC)5W(l-CN)Fe(dppe)(g-C5H5)]13 and [(g-C5H5)(dppe)Fe(l-
CN)Fe(dppe)(g-C5H5)]+.14 By contrast, the bridging cyanide
band for complexes 5+[BF4]−–8+[BF4]−, in which the C-bound
Ru(o-O2C6Cl4) unit has been oxidised, are ca. 6–8 cm−1
higher in energy than those of the neutral complexes 5–8, as
also found for trans-[(g-C5H5)(dppe)Fe(l-CN)Pt(py)2Cl]+,15
[(NC)5Fe(l-CN)Co(CN)5]6−,16 [(dppm)2(OC)Mn(l-CN)SnCl2]17
and [(dppm)2(OC)Mn(l-CN)CoCl3].18
Conclusions
The complexes [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-XY)MnL(NO)(g-
C5Me5)] (XY = CN or NC, L = CNBut or CNXyl) 1–4 and [(o-
O2C6Cl4)L(OC)2Ru(l-XY)M(CO)(PhC≡CPh)Tpꢀ] {XY = CN or
NC, M = Mo or W, L = PPh3 or P(OPh)3} 5–12 are oxidised first at
the ruthenium-bound catecholate ligand and then at Mn or M. In
both series, linkage isomers can be distinguished spectroscopically
and by their redox potentials.
Chemical oxidation gives the isolable monocations 1+–12+,
characterised as semiquinone complexes, i.e. the products of
catecholate-based oxidation. ESR spectroscopy serves to distin-
guish between linkage isomers, with larger 31P hyperfine coupling
constants for 2+, 5+ and 6+, in which the C-bound Ru(o-O2C6Cl4)
fragment is oxidised, than for 4+, 9+ and 10+. The latter, with
N-bound Ru(o-O2C6Cl4) fragments, also show small hyperfine
coupling to the nitrogen atom of the cyanide bridge.
ESR spectroscopy
The room temperature ESR spectra of 2+ (shown in Fig. 2 as
a representative example), 5+ and 6+ (Table 6) are similar to
those of [Ru(CN)(CO)2L(o-O2C6Cl4)]3 in showing a doublet due
to coupling to phosphorus {A(31P) = 16.6–21.7 G}, satellites due
to coupling to 99Ru and 101Ru (I = 5/2), and small coupling to
two of the chlorine atoms of the semiquinone ligand. For 4+,
9+ and 10+, isomers of 2+, 5+ and 6+ respectively, the spectra
are better simulated with an additional small coupling to 14N, in
agreement with oxidation of the N-bound Ru(CO)2L(o-O2C6Cl4).
In all cases, however, the spectra indicate the unpaired electron is
localised principally on the semiquinone, in agreement with the
IR spectroscopic and electrochemical data.
Experimental
The preparation, purification and reactions of the complexes
described were carried out under an atmosphere of dry nitro-
gen using deoxygenated solvents purified by using Anhydrous
Engineering double alumina or alumina–copper catalyst drying
columns. Reactions were monitored by IR spectroscopy. Unless
stated otherwise, complexes were purified using a mixture of two
solvents. The impure solid was dissolved in the more polar solvent,
the resulting solution was filtered and treated with the second
solvent, and the mixture was reduced in volume in vacuo to induce
precipitation. Unless stated otherwise, the complexes are air-stable
solids which dissolve in polar solvents such as CH2Cl2 or thf to
give moderately air-stable solutions.
11
The compounds [{Ru(CO)2L(l-o-O2C6Cl4)}2] {L = PPh3
or P(OPh)3 }, [Mo(CO)2(PhC≡CPh)Tpꢀ][PF6],9 [W(CO)2-
3
(PhC≡CPh)Tpꢀ][BF4],8 [MnX(CNR)(NO)(g-C5Me5)] (X = CN
or I, R = But5 or Xyl6), [M(CN)(CO)(PhC≡CPh)Tpꢀ] (M = Mo
or W)5 and [Fe(g-C5H4COMe)(g-C5H5)][BF4]19 were prepared by
published methods. The compound AgBF4 was purchased from
ACROS.
Fig.
2
(a) The experimental ESR spectrum of [(o-O2C6Cl4)-
(Ph3P)(OC)2Ru(l-CN)Mn(CNXyl)(NO)(g-C5Me5)]+ 2+ in CH2Cl2 at
294 K, and (b) the simulated spectrum using the parameters in Table 6.
The 31P hyperfine coupling constants for the PPh3 com-
plexes 4+ and 9+ {A(31P) = 8.7 G} are similar to those of
[(o-O2C6Cl4 )(Ph3P)(OC)2Ru(l-NC)Mn(CO)2(PEt3 )(dppe)-cis]+
IR spectra were recorded on a Perkin Elmer Spectrum One
FT Spectrometer fitted with a Perkin Elmer ZnSe universal ATR
sampling accessory. X-band ESR spectra were recorded on a
Bruker ESP300E spectrometer equipped with a Hewlett-Packard
5350B microwave frequency counter. The field calibration was
checked by measuring the resonance of the diphenylpicrylhydrazyl
(dpph) radical before each series of spectra. Spectra were simulated
using the Bruker Simfonia programme.
4
{A(31P) = 8.3 G} and [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)Re-
12
(CO)3(o-phen)]+ {A(31P) = 8.9 G} in which the N-bound frag-
ment is also oxidised. The larger values of 17.6 and 16.6 G for
2+ and 5+, with the C-bound Ru(o-O2C6Cl4) fragment, show that
A(31P) can be used to distinguish between linkage isomers. The
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Electrochemical studies were carried out using an EG & G
model 273A potentiostat linked to a computer using EG & G
Model 270 Research Electrochemistry software in conjunction
with a three-electrode cell. The auxiliary electrode was a platinum
wire and the working electrode a platinum disc (1.6 mm diam-
eter). The reference electrode was an aqueous saturated calomel
electrode separated from the test solution by a fine porosity frit and
an agar bridge saturated with KCl. Solutions in CH2Cl2 were 1.0 ×
solution was evaporated to dryness and the residue extracted with
toluene (20 cm3). The solution was filtered through Celite and
then reduced in volume to ca. 2 cm3 before n-hexane was added to
precipitate the product as a yellow solid, yield 60 mg (66%).
The complexes [(o-O2C6Cl4){(PhO)3P}(OC)2Ru(l-NC)Mo-
(CO)(PhC≡CPh)Tpꢀ] 10, [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)W-
(CO)(PhC≡CPh)Tpꢀ] 11 and [(o-O2C6Cl4){(PhO)3P}(OC)2Ru(l-
NC)W(CO)(PhC≡CPh)Tpꢀ] 12 were prepared similarly.
10−3 mol dm−3 in the compound and 0.1 mol dm−3 in [NBun ][PF6]
4
as the supporting electrolyte. Under these conditions, E◦ for the
ꢀ
[(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-CN)Mn(CNBut)(NO)-
(g-C5Me5)][BF4] 1+[BF4]−
one-electron oxidation of [Fe(g-C5Me5)2] or [Fe(g-C5H4COMe)(g-
C5H5)], added to the test solutions as internal calibrants, is −0.08
and 0.74 V respectively.
To
a
stirred solution of [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-
Microanalyses were carried out by the staff of the Microanalyt-
ical Service of the School of Chemistry, University of Bristol.
CN)Mn(CNBut)(NO)(g-C5Me5)] (60 mg, 0.06 mmol) in CH2Cl2
(20 cm3) was added [Fe(g-C5H4COMe)(g-C5H5)][BF4] (19 mg,
0.06 mmol). After 2 h, the purple solution was filtered, n-hexane
was added and the volume of solvent reduced in vacuo to complete
precipitation. The product was purified using CH2Cl2–n-hexane
to give a red-purple solid, yield 20 mg (31%).
[(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-CN)Mn(CNBut)-
(NO)(g-C5Me5)] 1
To a stirred solution of [NEt4][Ru(CN)(CO)2(PPh3)(o-O2C6Cl4)]
(45 mg, 0.05 mmol) in CH2Cl2 (20 cm3) was added
[MnI(CNBut)(NO)(g-C5Me5)] (26 mg, 0.06 mmol). After 4 h, the
solution was evaporated to dryness and the residue extracted with
toluene (15 cm3). The solution was filtered through Celite and
then reduced in volume to ca. 2 cm3 before n-hexane was added to
precipitate the product as a yellow solid, yield 25 mg (46%).
The complex [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-CN)Mn(CNXyl)-
(NO)(g-C5Me5)] 2 was prepared similarly.
The complex [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-CN)Mn(CNXyl)-
(NO)(g-C5Me5)][BF4] 2+[BF4]− was prepared similarly.
[(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)Mn(CNBut)(NO)-
(g-C5Me5)][BF4] 3+[BF4]−
To
a
stirred solution of [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-
NC)Mn(CNBut)(NO)(g-C5Me5)] (60 mg, 0.06 mmol) in CH2Cl2
(20 cm3) was added AgBF4 (11 mg, 0.06 mmol). After 10 min,
the red solution was filtered through Celite, n-hexane was added
and the volume of the solvent reduced in vacuo to complete
precipitation. The product was purified using CH2Cl2-n-hexane
to give a red-purple solid, yield 54 mg (83%).
[(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)Mn(CNBut)-
(NO)(g-C5Me5)] 3
To a stirred solution of [{Ru(CO)2(PPh3)(l-o-O2C6Cl4)}2] (41 mg,
0.03 mmol) in CH2Cl2 (25 cm3) was added [Mn(CN)-
(CNBut)(NO)(g-C5Me5)] (20 mg, 0.06 mmol). After 10 min, the
orange solution was filtered through Celite and the volume of
the filtrate reduced to ca. 3 cm3. n-Hexane was then added to
precipitate the product as an orange solid, yield 21 mg (34%).
The complex [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)Mn(CNXyl)-
(NO)(g-C5Me5)] 4 was prepared similarly.
The complex [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)Mn(CNXyl)-
(NO)(g-C5Me5)][BF4] 4+[BF4]− was prepared similarly.
[(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-CN)Mo(CO)-
(PhC≡CPh)Tpꢀ][BF4] 5+[BF4]−
To
a
stirred solution of [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-
CN)Mo(CO)(PhC≡CPh)Tpꢀ] (50 mg, 0.04 mmol) in CH2Cl2
(20 cm3) was added AgBF4 (7 mg, 0.04 mmol). After 30 min,
the purple solution was filtered through Celite, n-hexane was
added and the volume of solvent reduced in vacuo to complete
precipitation. The product was purified using CH2Cl2-n-hexane
to give a red-purple solid, yield 24 mg (44%).
[(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-CN)Mo(CO)(PhC≡CPh)Tpꢀ] 5
To a stirred solution of [Mo(CO)2(PhC≡CPh)Tpꢀ][PF6] (70 mg,
0.09 mmol) in CH2Cl2 (20 cm3) was added [NEt4][Ru(CN)-
(CO)2(PPh3)(o-O2C6Cl4)] (66 mg, 0.09 mmol). After 15 min, the
solution was evaporated to dryness and the residue extracted with
toluene (20 cm3). The solution was filtered through Celite and
then reduced in volume to ca. 2 cm3 before n-hexane was added to
precipitate the product as a yellow solid, yield 60 mg (54%).
The complexes [(o-O2C6Cl4){(PhO)3P}(OC)2Ru(l-CN)Mo-
(CO)(PhC≡CPh)Tpꢀ] 6, [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-CN)W-
(CO)(PhC≡CPh)Tpꢀ] 7 and [(o-O2C6Cl4){(PhO)3P}(OC)2Ru(l-
CN)W(CO)(PhC≡CPh)Tpꢀ] 8 were prepared similarly.
The complexes [(o-O2C6Cl4){(PhO)3P}(OC)2Ru(l-CN)Mo-
(CO)(PhC≡CPh)Tpꢀ][BF4] 6+[BF4]−, [(o-O2C6Cl4)(Ph3P)(OC)2-
Ru(l-CN)W(CO)(PhC≡CPh)Tpꢀ][BF4] 7+[BF4]− and [(o-O2C6-
Cl4){(PhO)3P}(OC)2Ru(l-CN)W(CO)(PhC≡CPh)Tpꢀ][BF4]
8+[BF4]− were prepared similarly.
[(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)Mo(CO)-
(PhC≡CPh)Tpꢀ][BF4] 9+[BF4]−
To
a
stirred solution of [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-
[(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)Mo(CO)(PhC≡CPh)Tpꢀ] 9
NC)Mo(CO)(PhC≡CPh)Tpꢀ] (50 mg, 0.04 mmol) in CH2Cl2
(20 cm3) was added AgBF4 (7 mg, 0.04 mmol). After 15 min, the
red solution was filtered through Celite, n-hexane was added and
the volume of solvent reduced in vacuo to complete precipitation.
To a stirred solution of [{Ru(CO)2(PPh3)(l-o-O2C6Cl4)}2] (50 mg,
0.04 mmol) in CH2Cl2 (25 cm3) was added [Mo(CN)-
(CO)(PhC≡CPh)Tpꢀ] (44 mg, 0.08 mmol). After 15 min, the yellow
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Table 7 Crystal and refinement data for [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-
NC)Mo(CO)(PhC≡CPh)Tpꢀ]·CH2Cl2 9·CH2Cl2
References
1 See, for example, F. L. Atkinson, N. C. Brown, N. G. Connelly, A. G.
Orpen, A. L. Rieger, P. H. Rieger and G. M. Rosair, J. Chem. Soc.,
Dalton Trans., 1996, 1959; N. C. Brown, G. B. Carpenter, N. G.
Connelly, J. G. Crossley, A. Martin, A. G. Orpen, A. L. Rieger, P. H.
Rieger and G. H. Worth, J. Chem. Soc., Dalton Trans., 1996, 3977;
K. M. Anderson, N. G. Connelly, E. Llamas-Rey, A. G. Orpen and
R. L. Paul, Chem. Commun., 2001, 1734; C. J. Adams, N. G. Connelly,
N. J. Goodwin, O. D. Hayward, A. G. Orpen and A. J. Wood, Dalton
Trans., 2006, 3584, and refs. therein.
2 Z. N. Chen, R. Appelt and H. Vahrenkamp, Inorg. Chim. Acta, 2000,
309, 65. See, for example, T. C. Holovics, S. F. Deplazes, M. Toriyama,
D. R. Powell, G. H. Lushington and M. V. Barybin, Organometallics,
2004, 23, 2927; A. B. P. Lever, Can. J. Chem., 2004, 82, 1102; S. Tanase
and J. Reedijk, Coord. Chem. Revs., 2006, 250, 2501; M. D. Ward,
Coord. Chem. Revs., 2006, 250, 3128; J. L. Boyer, M. L. Kuhlman and
T. B. Rauchfuss, Acc. Chem. Res., 2007, in press.
Compound
9·CH2Cl2
Formula
M
C58H49BCl6MoN7O5PRu
1375.53
Crystal system
Space group (no.)
Monoclinic
P2(1)/c (14)
14.730(5)
19.399(4)
21.653(4)
90
95.65(3)
90
173(2)
6157(3)
˚
a/A
˚
b/A
˚
c/A
a/◦
b/◦
c /◦
T/K
3
˚
U/A
Z
4
3 C. J. Adams, J. P. H. Charmant, N. G. Connelly, M. Gill, A. Kantacha,
S. Onganusorn and A. G. Orpen, Dalton Trans., in press.
4 A. Christofides, N. G. Connelly, H. J. Lawson, A. C. Loyns, A. G.
Orpen, M. O. Simmonds and G. H. Worth, J. Chem. Soc., Dalton
Trans., 1991, 1595.
l/mm−1
0.787
Reflections collected
Independent reflections (Rint
40302
14071 (0.1163)
0.0540, 0.1030
)
Final R indices [I > 2r(I)]: R1, wR
5 C. J. Adams, K. M. Anderson, M. Bardaji, N. G. Connelly, N. J.
Goodwin, E. Llamas-Rey, A. G. Orpen and P. H. Rieger, Dalton Trans.,
2004, 683.
6 S. Onganusorn, PhD Thesis, University of Bristol, 2006; C. J. Adams,
N. G. Connelly and S. Onganusorn, unpublished results.
7 J. L. Templeton, Adv. Organomet. Chem., 1989, 29, 1.
8 S. G. Feng, C. C. Philipp, A. S. Gamble, P. S. White and J. L. Templeton,
Organometallics, 1991, 10, 3504.
The product was purified using CH2Cl2-n-hexane to give a
red-purple solid, yield 45 mg (84%).
The complexes [(o-O2C6Cl4){(PhO)3P}(OC)2Ru(l-NC)Mo-
(CO)(PhC≡CPh)Tpꢀ][BF4] 10+[BF4]−, [(o-O2C6Cl4)(Ph3P)(OC)2-
Ru(l-NC)W(CO)(PhC≡CPh)Tpꢀ][BF4] 11+[BF4]− and [(o-O2C6-
Cl4){(PhO)3P}(OC)2Ru(l-NC)W(CO)(PhC≡CPh)Tpꢀ][BF4]
12+[BF4]− were prepared similarly.
9 C. J. Adams, I. M. Bartlett, S. Boonyuen, N. G. Connelly, D. J. Harding,
O. D. Hayward, E. J. L. McInnes, A. G. Orpen, M. J. Quayle and P. H.
Rieger, Dalton Trans., 2006, 3466.
10 C. J. Adams, I. M. Bartlett, S. Carlton, N. G. Connelly, D. J. Harding,
O. D. Hayward, A. G. Orpen, E. Patron, C. D. Ray and P. H. Rieger,
Dalton Trans., 2007, 62.
11 N. G. Connelly, I. Manners, J. R. C. Protheroe and M. W. Whiteley,
J. Chem. Soc., Dalton Trans., 1984, 2713.
12 M. Bardaji, N. C. Brown, N. G. Connelly, R. Davies, A. G. Orpen,
G. M. Rosair and N. R. Seear, J. Organomet. Chem., 1994, 474, C21.
13 N. Zhu and H. Vahrenkamp, Chem. Ber., 1997, 130, 1241.
14 G. Barrado, G. A. Carriedo, C. Diaz-Valenzuela and V. Riera, Inorg.
Chem., 1991, 30, 4416.
15 G. N. Richardson, U. Brand and H. Vahrenkamp, Inorg. Chem., 1999,
38, 3070.
16 R. E. Hester and E. M. Nour, J. Chem. Soc., Dalton Trans., 1981, 939.
17 K. M. Anderson, N. G. Connelly, N. J. Goodwin, G. R. Lewis, M. T.
Moreno, A. G. Orpen and A. J. Wood, J. Chem. Soc., Dalton Trans.,
2001, 1421.
18 N. G. Connelly, O. M. Hicks, G. R. Lewis, A. G. Orpen and A. J. Wood,
J. Chem. Soc., Dalton Trans., 2000, 1637.
19 N. G. Connelly and W. E. Geiger, Chem. Rev., 1996, 96, 877.
Crystal structure determination of [(o-O2C6Cl4)(Ph3P)(OC)2-
Ru(l-NC)Mo(CO)(PhC≡CPh)Tpꢀ]·CH2Cl2 9·CH2Cl2
Yellow-green crystals of [(o-O2C6Cl4)(Ph3P)(OC)2Ru(l-NC)-
Mo(CO)(PhC≡CPh)Tpꢀ]·CH2Cl2 9·CH2Cl2 were grown by allow-
ing diethyl ether to diffuse into a concentrated CH2Cl2 solution
of the complex at −10 ◦C. Many of the details of the structure
analysis are listed in Table 7.
CCDC reference number 633387.
For crystallographic data in CIF or other electronic format see
DOI: 10.1039/b700549k
Acknowledgements
We thank UUK for an ORS Postgraduate Scholarship (to S. O.).
1910 | Dalton Trans., 2007, 1904–1910
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