Reactions of [Ru5(µ5-C2PPh2) (µ-PPh2)(CO)13] with dimethyl disulfide. Synthesis of an open Ru5 cluster containing the dicarbon (C2) ligand and related chemistry
Abstract
The reaction between
[Ru
5
(µ
5
-C
2
PPh
2
)(µ-
PPh
2
)(CO)
13
] and Me
2
S
2
yielded
[Ru
5
(µ
5
-C
2
PPh
2
)(µ-
SMe)
2
(µ-PPh
2
)(CO)
13
] as the major
product. When heated the latter yielded the dicarbon complexes
[Ru
5
(µ
5
-C
2
)(µ-SMe)
2
(
µ-PPh
2
)
2
(CO)
12
] and
[Ru
5
(µ
5
-C
2
)(µ-SMe)
2
(
µ-PPh
2
)
2
(CO)
11
]. In large-scale
preparations of the latter four minor products were isolated: two
isomers of
[Ru
5
(µ
5
-C
2
PPh
2
)(µ-
SMe)
2
(µ-PPh
2
)(CO)
12
], the
tetranuclear complex
[Ru
4
(µ
4
-C
2
PPh
2
)(µ-
SMe)
2
(µ-PPh
2
)(CO)
10
] and
[Ru
5
(µ
5
-C
2
)(µ-SMe)
4
(
µ-PPh
2
)
2
(CO)
10
]. The latter is also
formed by direct reaction of
[Ru
5
(µ
5
-C
2
)(µ-SMe)
2
(
µ-PPh
2
)
2
(CO)
11
] with
Me
2
S
2
. All new complexes have been fully
characterised by single-crystal X-ray studies. In the three
Ru
5
(C
2
PPh
2
) complexes the
C
2
PPh
2
ligand acts as a seven-electron donor,
whereas in the Ru
4
complex it donates only five electrons to
the cluster. In the C
2
complexes, the different C–C
separations [between 1.26(2) and 1.305(5) Å] suggest a variable
degree of interaction with the metal core (electron donation and
back-bonding), the ligand formally donating either six or four electrons
to the cluster. This is borne out by the Ru–Ru separations,
average values of which range between 2.791 and 2.916 Å. The
conversion of
[Ru
5
(µ
5
-C
2
PPh
2
)(µ-
PPh
2
)(CO)
13
] into
[Ru
5
(µ
5
-C
2
)(µ-SMe)
2
(
µ-PPh
2
)
2
(CO)
11
] involves sequential
formation of several of these complexes, which reactions are
discussed.
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