SCHEDULED MAINTENANCE
Synthesis and characterisation of rhenium dithiocarbamate complexes. Crystal structures of [ReO{O(OH)C6H4}(S2CNEt 2)2], [Re{PPh2(C6H4S-2)}2 (S2CNEt2)]·Me2CO and [ReO{PPh(C6H4S-2)2}(S2 CNEt2)]
Abstract
The reaction of
[Re
2
O
3
(S
2
CNEt
2
)
4
]
with catechol in acetone yielded the dark orange complex
[ReO{O(OH)C
6
H
4
}(S
2
CNEt
2
)
2
] 1. The crystal structure shows a
distorted-octahedral geometry with the oxo group trans to the
monodentate catecholate ligand. The Re–O (catechol) bond length
is typical of a Re–O single bond and implies little
trans influence of the oxo ligand. Reaction of
[Re
2
O
3
(S
2
CNEt
2
)
4
]
with 1,4-dihydroxybenzene yielded the red-brown dimer
[{ReO(S
2
CNEt
2
)
2
}
2
(C
6
H
4
O
2
-1,4)] 2, in which the dianionic
ligand bridges two rhenium centres. With 2-amino-4-methylphenol
[ReO(OC
6
H
3
NH
2
-2-Me-4)(S
2
CNEt
2
)
2
] 3 was obtained containing the ligand
co-ordinated in a monodentate mode. Reaction of
[Re
2
O
3
(S
2
CNEt
2
)
4
]
with dithiolate proligands such as ethane-1,2-dithiol yielded
[NEt
2
H
2
][ReOL
2
],
L = C
2
H
4
S
2
-1,2 4,
C
6
H
4
S
2
-1,2 5 or
MeC
6
H
3
S
2
-3,4 6, where degradation of
the dithiocarbamate ligands to form the diethylammonium counter ion
occurs. Reaction of 1 with bidentate phosphines yielded green complexes
of the general formula
[Re(S
2
CNEt
2
)
2
L][BPh
4
], where
L = Me
2
PCH
2
CH
2
PMe
2
7 or Ph
2
PCH
2
CH
2
PPh
2
8. These reactions can be contrasted to the inactivity of these
phosphine ligands towards
[Re
2
O
3
(S
2
CNEt
2
)
4
]. The reaction of
[Re
2
O
3
(S
2
CNEt
2
)
4
]
with the bidentate phosphinothiolate proligand
PPh
2
(C
6
H
4
SH-2) in acetone at room
temperature yielded the red-orange rhenium(III) complex
[Re{PPh
2
(C
6
H
4
S-2)}
2
(S
2
CNEt
2
)]·Me
2
CO 9. The
crystal structure revealed a distorted-octahedral geometry. The sulfur
donors of the phosphinothiolate ligands adopt a cis
configuration. Reaction of
[Re
2
O
3
(S
2
CNEt
2
)
4
]
with the tridentate phosphinothiolate proligand
PPh(C
6
H
4
SH-2)
2
proceeded at room
temperature to yield the red rhenium(V) complex
[ReO{PPh(C
6
H
4
S-2)
2
}(S
2
CNEt
2
)] 10. Its crystal structure shows a
distorted-octahedral geometry. Reaction of
[Re
2
O
3
(S
2
CNEt
2
)
4
]
with SiMe
3
Cl yielded the new rhenium(V) precursor
[ReCl
2
(S
2
CNEt
2
)
2
][BPh
4
] 11 which permits investigation into rhenium dithiocarbamate
chemistry without an oxo core.
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