Alkylation of a dimolybdenum SO bridge, subsequent reactions, and characterization of the thioperoxide bridge.

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.

Activation of Ligand Reactivity: Thiolate C-S and Dithiophosphate Ester C-O Heterolyses within a Dimolybdenum(V) System.

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.