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

Abstract

The reactions of the p-tolyliminooxosulphurane complexes [Ru(CO)(L)(PPh3)2 (OSNR)] (L=CO, CNC6H3Me-2,6, CNtBu; R=C6H4Me-4 (p-tolyl)) and [OsCl(NO)(PPh3)2(OSNR)] with a range of electrophiles have been investigated: [Ru(CO)(CNC6H3Me2-2,6)(PPh3)2(OSNR)] reacts with hexafluoroantimonic acid to give the N-protonated salt [Ru(OSNHR)(CO)(CNC6H3Me2-2,6)(PPh3)2]SbF6, which in turn reacts with nucleophilic ligands CNtBu and SCN- to give the η1-sulphinamido complexes [Ru(OSNHR)(CO)(CNtBu)(CNC6H3Me2-2,6)(PPh3)2]+ and [Ru(OSNHR)(SCN)(CO)(CNC6H3Me2-2,6)(PPh3)2]. Alkylation of [Ru(CO)(L)(PPh3)2(OSNR)] with R′X occurs at oxygen, giving the complexes [Ru(R′OSNR)(CO)(L)(PPh3)2]X (L=CNC6H3Me2-2,6, R′=CH3, X=CF3SO3; R′=C2H5, X=SO3F; L=CO, R′=CH3, X=CF3SO3). Silylation of [Ru(CO)(CNC6H3Me2-2,6)(PPh3)2(OSNR)] with Me3SiOSO2CF3 occurs at oxygen, to give [Ru(Me3SiOSNR)(CO)(CNC6H3Me2-2,6)(PPh3)2]O3SCF3 whilst [OsCl(NO)(PPh3)2(OSNR)] with BF3OEt2 gives [OsCl(NO)(PPh3)2(F3BOSNR)]. The adducts formed by reactions 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. Show more