Alkylation of a Dimolybdenum SO Bridge, Subsequent
Reactions, and Characterization of the Thioperoxide Bridge

Tuong, Chi Minh; Hammons, Whitney K.; Howarth, Ashley L.; Lutz, Kelly E.; Maduvu, Ackim D.; Haysley, Laura B.; R. T. Allred, Brian; Hoyt, Lenore K.; Mashuta, Mark S.; Noble, Mark E.

doi:10.1021/ic9002093.s001

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Alkylation of a Dimolybdenum SO Bridge, Subsequent Reactions, and Characterization of the Thioperoxide Bridge

journal contribution

posted on 2009-06-01, 00:00 authored by Chi Minh Tuong, Whitney K. Hammons, Ashley L. Howarth, Kelly E. Lutz, Ackim D. Maduvu, Laura B. Haysley, Brian R. T. Allred, Lenore K. Hoyt, Mark S. Mashuta, Mark E. Noble

The SO bridge of the complex, [Mo₂(NTo)₂(S₂P(OEt)₂)₂(μ-O₂CMe)(μ-SBn)(μ-SO)], 1, displayed nucleophilicity at O, giving alkylation products [Mo₂(NTo)₂(S₂P(OEt)₂)₂(μ-O₂CMe)(μ-SBn)(μ-SOR)]⁺, 4⁺, which contained the thioperoxide bridge. These cations were then subject to nucleophilic attack by two pathways. Debenzylation of the bridge thiolate in 4⁺ afforded neutral [Mo₂(NTo)₂(S₂P(OEt)₂)₂(μ-O₂CMe)(μ-S)(μ-SOR)], 5; de-esterification of a dithiophosphate ligand in 4⁺ gave [Mo₂(NTo)₂(S₂P(O)(OEt))(S₂P(OEt)₂)(μ-O₂CMe)(μ-SBn)(μ-SO)], 6, which contained a monoester, dithiophosphate ligand. Complex 1 gave a slow and clean reaction in the crystalline state, further demonstrating its nucleophilicity by attacking a neighboring molecule in its lattice. X-ray crystallography confirmed the thioperoxide linkage and revealed structural similarities of the Mo₂(μ-SOR) unit to sulfenate esters (RSOR) and related derivatives.