TRANSITION-METAL COMPLEXES WITH SULFUR LI GANDS .108. A FACILE SYNTHESIS OF THE TERTIARY AMINE-THIOLATO LIGAND 'S(2)N(2)ME(2)'(2-) - INFLUENCE OF THE AMINOMETHYLATION ON THE COORDINATION CHEMISTRY OF NICKEL AND RUTHENIUM COMPLEXES WITH [M('S(2)N(2)R(2)')] FRAMEWORKS (R=H, CH3) -MINO-N,N'-DIMETHYL-N,N'-BIS(2-BENZENETHILATO)(2-))

In a single pot synthesis consecutive reaction of the tetradentate ami ne-thiole H-2-'S2N2H2' 2 ('S2N2H2'2- = ,2-ethanediamino-N,N'-bis(2-ben zenethiolato)(2-)), with [LiN(SiMe(3))(2)] and benzyl chloride (BzCl) yields the amine-thioether 'Bz(2)S(2)N(2)H(2)' which gives the tertiar y amine-thioether 'Bz(2)S(2)N(2)Me(2)' when reacted with further [LiN( SiMe(3))(2)] and CH3I. Removal of the benzyl groups with an excess of sodium and acidification with hydrochloric acid finally yield H-2-'S(2 )N(2)Me(2)' 1 ('SNMe2'2- = no-N,N'-dimethyl-N,N'-bis(2-benzenethiolato )(2-)). 1 and 2 have been characterized by X-ray structure analysis. W ith [Ni(CH3COO)(2)]. 4H(2)O, 1 yields racemic [Ni('S(2)N(2)Me(2)')] 3 in a diastereospecific reaction. Crystallization of 3 leads to spontan eous resolution of the racemate. By X-ray structure analysis of 3 the absolute configuration in the single crystal examined was determined u sing Roger's mu-refinement (mu = 1.00(4)). Upon reaction with [RuCl3 . 3H(2)O], LiOMe and CO, 1 yields [Ru(CO)(2)('S(2)N(2)Me(2)')] 5. Spect roscopic data indicate that 5 and the parent complex [Ru(CO)(2)('S2N2H 2')] differ with respect to their core structures. Influence of the am ine methylation on structure and reactivity of complexes with [M('S(2) N(2)R(2)')] cores, R = H, Me, is discussed.