title: 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-S)] core topology very similar to the P(N) cluster of nitrogenase. The reaction system 1/Et4NOH in acetonitrile/methanol yields the P(N)-type cluster [(Tp)2Mo2Fe6S9(OMe)2(H2O)](3-) (5). The system 1/Me3SnOH/F- affords the oxo-bridged double P(N)-type cluster {[(Tp)2Mo2Fe6S9(mu2-O)]2}5- (7), convertible to the oxidized cluster {[(Tp)2Mo2Fe6S9(mu2-O)]2}4- (6), which is prepared independently from [(Tp)2Mo2Fe6S9F2(H2O)](3-)/(Bu3Sn)2O. In the preparations of 3-5 and 7, hydroxide liberates sulfide from 1 leading to the formation of P(N)-type clusters. Unlike reactions with HQ-, no oxygen atoms are integrated into the core structures of the products. However, the half-dimer composition [Mo2Fe6S9O] relates to the MoFe7S9 constitution of the putative native cluster with X = O. (Tp = hydrotris(pyrazolyl) borate(1-)).
authors: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, USA.
authors: Mark L
authors: ML
authors: Hlavinka
authors: Taichi
authors: T
authors: Miyaji
authors: Richard J
authors: RJ
authors: Staples
authors: R H
authors: RH
authors: Holm
mesh_terms: D006878:Hydroxides / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008982:Molybdenum / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization; D013455:Sulfur / Q000737:chemistry*
chemical_list: D006878:Hydroxides; D013455:Sulfur; D008982:Molybdenum; D007501:Iron; D010100:Oxygen