title: Activation of Ligand Reactivity: Thiolate C-S and Dithiophosphate Ester C-O Heterolyses within a Dimolybdenum(V) System.
abstract: Ligand reactivity was demonstrated for sulfide alkylation, thiolate dealkylation, and dithiophosphate de-esterification within molybdenum(V) dimers. The cationic complex [Mo(2)(NC(6)H(4)Me)(2)(S(2)P(OEt)(2))(2)(&mgr;-O(2)CMe)(&mgr;-SR)(2)](+) was inductively activated toward thiolate C-S and dithiophosphate C-O heterolyses. The dealkylations were studied using anionic nucleophiles, and various reactivity patterns were characterized. The de-esterification of the diethyl dithiophosphate ligands produced complexes containing the rare monoester EtO(O)PS(2)(2)(-) ligand. This ligand's phosphoryl group was poorly nucleophilic but weakly basic. Crystallographic comparisons between the activated cation and the neutral complex [Mo(2)(NC(6)H(4)Me)(2)(S(2)P(OEt)(2))(2)(&mgr;-O(2)CMe)(&mgr;-S)(&mgr;-SMe)] were conducted to delineate structural differences related to the activation. A crystallographic study was also done of the complex [Mo(2)(NC(6)H(4)CH(3))(2)(S(2)P(OEt)(2))(S(2)P(O)OEt)(&mgr;-O(2)CMe)(&mgr;-SEt)(2)], which provided internal comparison of monoester EtO(O)PS(2)(2)(-) and diester (EtO)(2)PS(2)(-) ligand types.
authors.affiliation: Department of Chemistry, University of Louisville, Louisville, Kentucky 40292.
authors.forename: Edith I.
authors.initials: EI
authors.lastname: Koffi-Sokpa
authors.forename: D. Troy
authors.initials: DT
authors.lastname: Calfee
authors.forename: Brian R. T.
authors.initials: BR
authors.lastname: Allred
authors.forename: Jackie L.
authors.initials: JL
authors.lastname: Davis
authors.forename: Elaine K.
authors.initials: EK
authors.lastname: Haub
authors.forename: Alexis K.
authors.initials: AK
authors.lastname: Rich
authors.forename: Richard A.
authors.initials: RA
authors.lastname: Porter
authors.forename: Mark S.
authors.initials: MS
authors.lastname: Mashuta
authors.forename: John F.
authors.initials: JF
authors.lastname: Richardson
authors.forename: Mark E.
authors.initials: ME
authors.lastname: Noble