Reaction of a dicarbon Ru5 cluster with CO: crystal structures of [Ru5(µ4-C2)(µ-SMe)2( µ-PPh2)2(CO)13] and [Ru4(µ4-C2)(µ-SMe)2( µ-PPh2)2(CO)10]
Abstract
The reaction between
[Ru
5
(µ
5
-C
2
)(µ-SMe)
2
(
µ-PPh
2
)
2
(CO)
11
] 1 and CO (30
atm) yielded
[Ru
5
(µ
4
-C
2
)(µ-SMe)
2
(
µ-PPh
2
)
2
(CO)
13
] 2 and
[Ru
4
(µ
4
-C
2
)(µ-SMe)
2
(
µ-PPh
2
)
2
(CO)
10
] 3, both
characterised by single-crystal X-ray crystallography. In 2,
addition of 2
CO results in the net cleavage of two Ru–Ru
bonds and expansion of the resulting Ru
3
cluster. The
C
2
ligand bridges one edge of the Ru
3
core and the
isolated Ru–Ru bonded fragment in a
µ,µ-η
1
,η
2
mode, albeit with asymmetric
Ru–C
2
π interactions. In 3, one Ru atom has
been excised from the cluster present in 1. One Ru–Ru bond
is bridged by two SMe groups as a result of migration of one of these.
Although the C
2
ligand bridges all four metal atoms, only two
Ru – Ru bonds are present, with the non-bonded
Ru · · · Ru vector being
bridged by PPh
2
. Extended-Hückel molecular orbital
calculations have been used to rationalise the observed structures.
CO results in the net cleavage of two Ru–Ru
bonds and expansion of the resulting Ru
3
cluster. The
C
2
ligand bridges one edge of the Ru
3
core and the
isolated Ru–Ru bonded fragment in a
µ,µ-η
1
,η
2
mode, albeit with asymmetric
Ru–C
2
π interactions. In 3, one Ru atom has
been excised from the cluster present in 1. One Ru–Ru bond
is bridged by two SMe groups as a result of migration of one of these.
Although the C
2
ligand bridges all four metal atoms, only two
Ru – Ru bonds are present, with the non-bonded
Ru · · · Ru vector being
bridged by PPh
2
. Extended-Hückel molecular orbital
calculations have been used to rationalise the observed structures.
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