Six-co-ordinate 1,2-dithiolene complexes of tungsten(II) of the type [W(S–S)(CO)2L2] [S–S = C3S5, benzene-1,2-dithiolate or maleonitriledithiolate; L2 = (PPh3)2, (PEt3)2 or Ph2P(CH2)2PPh2]
Abstract
Reaction of the complexes
[WI
2
(CO)
3
L
2
]
[L
2
= (PEt
3
)
2
,
(PPh
3
)
2
or
Ph
2
P(CH
2
)
2
PPh
2
=
dppe] with 1 equivalent of Na
2
[S–S]
(S–S = C
3
S
5
or
maleonitriledithiolate) or H
2
bdt (benzene-1,2-dithiol) in
acetonitrile and ethanol at room temperature afforded good yields of the
six-co-ordinate compounds [W(S–S)(CO)
2
L
2
]
by displacement of the iodide ligands and a carbonyl ligand. X-Ray
crystallographic studies were carried out on
[W(S–S)(CO)
2
L
2
]
[S–S = C
3
S
5
,
L
2
= (PEt
3
)
2
;
S–S = bdt,
L
2
= (PEt
3
)
2
or
L
2
= dppe]. The three structures are all
six-co-ordinate with geometries intermediate between octahedral and
trigonal prismatic but closer to the latter.
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