The subvalent mercury cluster
[dmpm = bis(dimethylphosphino)methane], involving the +4/3
oxidation state of mercury, was formed by reaction of
with 2 equivalents of dmpm or by reduction
of a mixture of
and dmpm in the molar ratio 2∶4 with elemental Hg. The
cation consists of a Hg
triangle [Hg–Hg 276.68(14),
280.99(14) and 295.53(14) pm] in which two edges are bridged by one dmpm
ligand and the third edge is doubly bridged by a pair of dmpm ligands.
The three Hg atoms and the phosphorus atoms of the singly bridging dmpm
ligands are nearly in a plane. The dihedral angles of the Hg
triangle and the mean planes formed by the doubly bridged Hg atoms and
the phosphorus atoms of the two bridging dmpm ligands respectively are
61 and 46°. The complex is fluxional on the
time-scale at 81 MHz at ambient temperature due to intramolecular
exchange between the two different types of dmpm ligands.
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Journal of the Chemical Society, Dalton Transactions
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