SCHEDULED MAINTENANCE
Seven co-ordinate macrocyclic tetrathioether complexes of molybdenum(II) and tungsten(II)
Abstract
Treatment of [{Mo(µ-Br)Br(CO)
4
}
2
]
with 3,3,7,7,11,11,15,15-octamethyl-1,5,9,13-tetrathiacyclohexadecane
(Me
8
[16]aneS
4
) in CH
2
Cl
2
gave the crystallographically characterised, seven-co-ordinate, ionic
complex
[MoBr(CO)
2
(Me
8
[16]aneS
4
)][MoBr
3
(CO)
4
] 1. Reaction of 2 equivalents of
[MI
2
(CO)
3
(NCMe)
2
] (M = Mo
or W) with 1 equivalent of Me
8
[16]aneS
4
afforded
the analogous iodo-complex
[MoI(CO)
2
(Me
8
[16]aneS
4
)][MoI
3
(CO)
4
] 2 and the crystallographically
characterised complexes
[WI(CO)
2
(Me
8
[16]aneS
4
)][WI
3
(CO)
4
] 3 and
[WI(CO)
3
(Me
8
[16]aneS
4
)][WI
3
(CO)
4
] 4. The cations in complexes 1 and
3 have distorted capped-trigonal-prismatic geometries whereas
that in 4 has a geometry lying between capped octahedral and
capped trigonal prismatic. The anions of all three complexes have
capped-octahedral geometries. Treatment of 2 equivalents of
[MI
2
(CO)
3
(NCMe)
2
] with 1 equivalent of
1,5,9,13-tetrathiacyclohexadecane ([16]aneS
4
),
1,4,8,11-tetrathiacyclotetradecane ([14]aneS
4
) or
1,4,7,10-tetrathiacyclododecane ([12]aneS
4
) yielded the
bimetallic thioether-bridged complexes
[M
2
I
4
(CO)
6
([n]aneS
4
-S,S′,S″,S
‴)] (n = 16,
M = Mo; n = 14,
M = Mo or W; n = 12,
M = Mo), and the ionic complexes
[WI(CO)
2
([n]aneS
4
)][WI
3
(CO)
4
] (n = 16 or 12). The relationships
between the various products of these reactions are discussed. Reaction
of [16]aneS
4
with [MoCl
3
(thf)
3
]
(thf = tetrahydrofuran) gave a polymeric complex of
empirical formula
[Mo
3
Cl
9
([16]aneS
4
)
2
] plus
the dinuclear, ionic complex
[Mo
2
Cl
5
([16]aneS
4
-S,S
′)
2
]Cl.
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