Structural diversity of tetranuclear tungsten sulfide clusters: syntheses and crystal structures of clusters containing raft-type W4(µ3-S)2(µ-S)4 and tetrahedral W4(µ-S)6 cores
Abstract
Reaction of
cis-[W(N
2
)
2
(PMe
2
Ph)
4
] 1 with 2 equivalents of (Me
3
Si)
2
S
in the presence of an excess of MeOH gave a tetranuclear tungsten
sulfide cluster
[W
4
(µ
3
-S)
2
(µ-S)
4
(SH)
2
(PMe
2
Ph)
6
] 2. Substitution of
chloride anions for the terminal SH ligands in 2 took place on
reaction with 1 equivalent of SnCl
2
, giving the isostructural
W
4
cluster
[W
4
(µ
3
-S)
2
(µ-S)
4
Cl
2
(PMe
2
Ph)
6
] 3. Both 2
and 3 with ten skeletal electrons consist of an almost
equilateral raft-type W
4
framework with five
metal–metal bonds. On treatment with 2.4–3 equivalents of
AgOSO
2
CF
3
, compound 3 underwent
two-electron oxidation to give
[W
4
(µ
3
-S)
2
(µ-S)
4
Cl
2
(PMe
2
Ph)
6
][OSO
2
CF
3
]
2
4, which has a distorted raft-type
W
4
core owing to the presence of only eight skeletal
electrons. On the other hand, reduction of 3 with an excess of
Na/Hg resulted in formation of the twelve-skeletal-electron cluster
[W
4
(µ-S)
6
(PMe
2
Ph)
4
]
5 containing a tetrahedral W
4
core with six
W–W bonds. The detailed structures of 2–5
were determined by single-crystal X-ray diffraction.
Please wait while we load your content...
