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. 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.
Koffi-Sokpa
Edith I.
EI
Department of Chemistry, University of Louisville, Louisville, Kentucky 40292.
Calfee
D. Troy
DT
Allred
Brian R. T.
BR
Davis
Jackie L.
JL
Haub
Elaine K.
EK
Rich
Alexis K.
AK
Porter
Richard A.
RA
Mashuta
Mark S.
MS
Richardson
John F.
JF
Noble
Mark E.
ME