title: Alkylation of a dimolybdenum SO bridge, subsequent reactions, and characterization of the thioperoxide bridge.
abstract: The SO bridge of the complex, [Mo(2)(NTo)(2)(S(2)P(OEt)(2))(2)(mu-O(2)CMe)(mu-SBn)(mu-SO)], 1, displayed nucleophilicity at O, giving alkylation products [Mo(2)(NTo)(2)(S(2)P(OEt)(2))(2)(mu-O(2)CMe)(mu-SBn)(mu-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 [Mo(2)(NTo)(2)(S(2)P(OEt)(2))(2)(mu-O(2)CMe)(mu-S)(mu-SOR)], 5; de-esterification of a dithiophosphate ligand in 4(+) gave [Mo(2)(NTo)(2)(S(2)P(O)(OEt))(S(2)P(OEt)(2))(mu-O(2)CMe)(mu-SBn)(mu-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 Mo(2)(mu-SOR) unit to sulfenate esters (RSOR) and related derivatives.
authors.affiliation: Department of Chemistry, University of Louisville, Louisville, Kentucky 40292, USA.
authors.forename: Chi Minh
authors.initials: CM
authors.lastname: Tuong
authors.forename: Whitney K
authors.initials: WK
authors.lastname: Hammons
authors.forename: Ashley L
authors.initials: AL
authors.lastname: Howarth
authors.forename: Kelly E
authors.initials: KE
authors.lastname: Lutz
authors.forename: Ackim D
authors.initials: AD
authors.lastname: Maduvu
authors.forename: Laura B
authors.initials: LB
authors.lastname: Haysley
authors.forename: Brian R T
authors.initials: BR
authors.lastname: Allred
authors.forename: Lenore K
authors.initials: LK
authors.lastname: Hoyt
authors.forename: Mark S
authors.initials: MS
authors.lastname: Mashuta
authors.forename: Mark E
authors.initials: ME
authors.lastname: Noble
mesh_terms: D000478:Alkylation; D018360:Crystallography, X-Ray; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry*; D010545:Peroxides / Q000737:chemistry*; D013237:Stereoisomerism; D013455:Sulfur / Q000737:chemistry*
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D010545:Peroxides; D013455:Sulfur; D008982:Molybdenum; D010100:Oxygen