Cd. Borman et al., MECHANISTIC STUDIES ON NOVEL MO-S CONTAINING CLUSTER COMPLEXES IN AQUEOUS-SOLUTION, Pure and applied chemistry, 67(2), 1995, pp. 305-310
Studies on Mo-S cluster complexes including cuboidal [Mo4S4H2O)12]n+ (
n = 4,5,6) and heterometallic [Mo3MS4(H2O)x]4+ (x = 10, 12) complexes
are described. Such cubes are stable in aqueous solution, and provide
a ready means of studying redox and substitution reactions not possibl
e in the case of e.g. Fe4S4 complexes. Here the emphasis is on substit
ution reactions. Studies on two heterometallic cubes M = Ni, Cr obtain
ed from [Mo3S4(H2O)9]4+ are reported. Whereas [Mo3NiS4(H2O)10]4+ conta
ins tetrahedral Ni, the [Mo3CrS4(H2O)12]4+ cluster has octahedral Cr.
Using the tridentate 1,4,7-triazacyclononane ligand, 9-aneN3, the cube
[Mo3Ni(9-aneN3)S4(H2O)9]4+ has been prepared containing an octahedral
and inert Ni. The case for a Ni-degrees assignment is considered. The
crystallographically characterised [Mo3S7Br6]2- has been converted to
a new aqua ion [Mo3S7(H2O)6]4+. With P(C6H4SO3)3(3-) in 2M Hpts the l
atter gives [Mo3S4(H2O)9]4+. Two stages are observed in substitution s
tudies with NCS-.