Hydroxide-promoted core conversions of molybdenum-iron-sulfur edge-bridged double cubanes: oxygen-ligated topological PN clusters.

ABSTRACT: The occurrence of a heteroatom X (C, N, or O) in the MoFe7S9X core of the iron-molybdenum cofactor of nitrogenase has encouraged synthetic attempts to prepare high-nuclearity M-Fe-S-X clusters containing such atoms. We have previously shown that reaction of the edge-bridged double cubane [(Tp)2Mo2Fe6S8(PEt3)4] (1) with nucleophiles HQ- affords the clusters [(Tp)2Mo2Fe6S8Q(QH)2](3-) (Q = S, Se) in which HQ- is a terminal ligand and Q(2-) is a mu2-bridging atom in the core. Reactions with OH- used as such or oxygen nucleophiles generated in acetonitrile from (Bu3Sn)2O or Me3SnOH and fluoride were examined. Reaction of 1 with Et4NOH in acetonitrile/water generates [(Tp)2Mo2Fe6S9(OH)2]3- (3), isolated as [(Tp)2Mo2Fe6S9(OH)(OC(=NH)Me)(H2O)](3-) and shown to have the [Mo2Fe6(mu2-S)2(mu3-S)6(mu6-

SUBMITTER: Hlavinka ML 

PROVIDER: S-EPMC2527064 | biostudies-literature | 2007 Oct

REPOSITORIES: biostudies-literature