GA Lawrance

Jr GP Haight

KM Rahmoeller

MR Snow

NC Howlader

TW Hambley

The anionic molybdenum(IV)
cluster [Mo3S4(CN)9]5- has been
subjected to X-ray crystal structure analysis. The potassium salt crystallized
in the triclinic space group P1, a
10.634(1), b 11.888(3), c 24.892(2) �, α 89.56(2), β
79.86(1), γ 76.53(2)�, Z 4. The three MoIV atoms in each unit
of approximately CSL3v symmetry are situated at the corners of an
equilateral triangle with Mo-Mo distance 2.765(7) �. There are three S2-
ligands bridging between pairs of Mo atoms, and a unique S2- ligand
located uniformly above the plane of the equilateral triangle. Distorted
octahedral coordination of each MoIV is
completed by three CN- ligands to each of the three metal centres.
The ion is structurally similar to the [MO3S(S2)6]2-
precursor, and to [Mo3O4X9]n-
analogues. In dimethyl sulfoxide, the cluster is irreversibly reduced in a
single step near -2 V (v. saturated calomel electrode), but exhibits a
quasi-reversible oxidation at + 0.51 V. On the coulometric
time scale, the complex is irreversibly oxidized to MoV
monomer.</jats:p

Structure and redox properties of the molybdenum(IV) metal cluster K5[Mo3S4(CN)9].7H2O

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