Synthesis of protonated carboxylato and trifluoromethanesulfonato derivatives of vanadium(II) by redox reactions on bis(mesitylene)vanadium(0)
Abstract
Bis(mesitylene)vanadium(0), V(mes)
2
, underwent a
two-electron redox process in heptane with CF
3
SO
3
H
affording the vanadium(II) derivative
[V(CF
3
SO
3
)
2
(CF
3
SO
3
H)], an example of a co-ordination compound containing both the
acid and its conjugated base in its composition. The vanadium(0) complex
and CF
3
CO
2
H gave a product resulting from a
one-electron transfer process, namely
[V(mes)
2
][CF
3
CO
2
]. This compound, which
dissolves unchanged in neat
CF
3
CO
2
H–(CF
3
CO)
2
O,
evolves to the vanadium(II) derivative
[H(thf
)
n
][V(CF
3
CO
2
)
3
] (thf = tetrahydrofuran) by addition of
tetrahydrofuran. Deprotonation of the vanadium(II) complexes
occurs in the presence of thf or heterocyclic nitrogen bases to form the
ionic derivatives [HB][VA
3
], B = thf or a
heterocyclic nitrogen base;
A = CF
3
SO
3
or
CF
3
CO
2
. The trifluoroacetato derivative
[H(thf)
n
][V(CF
3
CO
2
)
3
] undergoes methylation with CH
2
N
2
to
the vanadium(II) ester adduct
[V(CF
3
CO
2
)
2
(CF
3
CO
2
CH
3
)], and is oxidized to the vanadium(III)
trifluoroacetato derivatives
[V(CF
3
CO
2
)
3
] and
[V(CF
3
CO
2
)
2
C
14
H
8
O
2
] by benzoyl peroxide (or dioxygen) and
9,10-phenanthrenedione, respectively.
)
n
][V(CF
3
CO
2
)
3
] (thf = tetrahydrofuran) by addition of
tetrahydrofuran. Deprotonation of the vanadium(II) complexes
occurs in the presence of thf or heterocyclic nitrogen bases to form the
ionic derivatives [HB][VA
3
], B = thf or a
heterocyclic nitrogen base;
A = CF
3
SO
3
or
CF
3
CO
2
. The trifluoroacetato derivative
[H(thf)
n
][V(CF
3
CO
2
)
3
] undergoes methylation with CH
2
N
2
to
the vanadium(II) ester adduct
[V(CF
3
CO
2
)
2
(CF
3
CO
2
CH
3
)], and is oxidized to the vanadium(III)
trifluoroacetato derivatives
[V(CF
3
CO
2
)
3
] and
[V(CF
3
CO
2
)
2
C
14
H
8
O
2
] by benzoyl peroxide (or dioxygen) and
9,10-phenanthrenedione, respectively.
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