Copper complexes of 1,3-bis(2-pyridyl)-1-thiapropane (bpt) and pyridine-2(1H)-thione. Crystal structure of [{Cu(µ-O2CMe)2(bpt)}2 ] and metal-promoted cleavage of bpt
Abstract
The reactivity of the asymmetric thioether
1,3-bis(2-pyridyl)-1-thiapropane
[1-(2-pyridyl)-2-(2-pyridylsulfanyl)ethane] (bpt) with
copper-(I) and -(II) starting materials has been
investigated. Reaction with [Cu(NCMe)
4
]PF
6
in MeCN
gave a cluster formulated as
[Cu
4
(bpt)
6
][PF
6
]
4
, whilst
reaction in tetrahydrofuran resulted in partial cleavage of bpt to give
the mixed thionato–thioether complex
[Cu
2
(SC
5
H
4
N)(bpt)]PF
6
[SC
5
H
4
NH = pyridine-2(1H)-
thione]. Reaction with
[Cu
2
(µ-O
2
CMe)
4
] in MeOH gave
the dimer
[{Cu(µ-O
2
CMe)
2
(bpt)}
2
], whose crystal structure shows that the bpt ligands are
monodentate and co-ordinated via the N atom remote from the
thioether. The compound bpt undergoes cleavage with other
copper(II) salts such as Cu(BF
4
)
2
,
ultimately giving the hexameric copper(I) complex
[Cu
6
(SC
5
H
4
N)
6
]. The details
of this reaction have been investigated. Reaction of
SC
5
H
4
NH with Cu(NO
3
)
2
in the
presence of HNO
3
gave
[Cu(NO
3
)(SC
5
H
4
NH)
2
], which
in turn reacted progressively with PPh
3
to give
[Cu(NO
3
)(SC
5
H
4
NH)
2
(PPh
3
)] and the known complex
[Cu(SC
5
H
4
NH)
2
(PPh
3
)
2
]NO
3
, whose crystal structure has been determined.
Other complexes of SC
5
H
4
NH with
copper(I) and a range of anions have been prepared, and the
crystal structure of the dimer
[Cu
2
(SC
5
H
4
NH)
6
][MeC
6
H
4
SO
3
]
2
is reported.
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