The coordination chemistry of iminooxosulphuranes VII. Coordinative activation of tolyliminooxosulphurane towards electrophiles

Article abstract of DOI:10.1016/0022-328X(90)85278-7

The reactions of the p-tolyliminooxosulphurane complexes (L = CO, CNC6H3Me-2,6, CN^tBu; R = C6H4Me-4 (p-tolyl) and with a range of electrophiles have been investigated: reacts with hexafluoroantimonic acid to give the N-protonated salt SbF6, which in turn reacts with nucleophilic ligands CN^tBu and SCN^- to give the η¹-sulphinamido complexes tBu)(CNC6H3Me2-2,6)(PPh3)2>⁺and .Alkylation of with R'X occurs at oxygen, giving the complexes X (L = CNC6H3Me2-2,6, R' = CH3, X = CF3SO3; R' = C2H5, X = SO3F; L = CO, R' = CH3, X = CF3SO3).Silylation of with Me₃SiOSO₂CF₃ occurs at oxygen, to give O3SCF3 whilst with BF3OEt2 gives .The adducts formed by reaction of coordinated iminooxosulphuranes with HSbF6, Me3SiOSO2CF3 and BF3OEt2 reacted with KOH/MeOH, CsF and acetone, respectively to regenerate the zerovalent iminooxosulphurane complexes, but alkylation was found to be irreversible.