Ubergangsmetallkomplexe mit Schwefelliganden, CVIII+. Eine bequeme Synthese des tertiären Amin-thiolat-Liganden 'S2N2Me2'2_. Einfluß der Aminmethylierung

In a single pot synthesis consecutive reaction o f the tetradentate am ine-thiole H 2 ' S 2 N 2 H 2' 2 ('S 2 N 2 H 2'2= l,2 -e th an ed iam in o-N ,N '-b is(2 -b en zen eth io la to )(2 -)), with [L iN (SiM e3)2] and benzyl chloride (BzC l) yields the am ine-thioether 'B z2 S2 N 2 H 2' which gives the tertiary am ine-thioether 'Bz2 S2 N 2 M e2' when reacted with further [L iN (SiM e3)2] and C H 3 I. Rem oval o f the benzyl groups with an excess o f sodium and acidification with hydrochloric acid finally yield H 2 ' S 2 N 2 M e2' 1 ('S 2 N 2M e2'2~ = l,2-ethaned iam ino-N ,N '-dim eth yl-N ,N '-b is(2 -b en zen eth io la to )(2 -)). 1 and 2 have been characterized by X-ray structure analysis. With [N i(C H 3 C O O )2 ] -4 H 2 0 , 1 yields racemic [N i('S 2 N 2 M e2')] 3 in a diastereospecific reaction. Crystallization o f 3 leads to spontaneous resolution o f the racem ate. By X-ray structure analysis o f 3 the absolute configuration in the single crystal exam ined was determ i­ ned using R oger's //-refinem ent (// = 1.00(4)). U pon reaction with [RuCl3 -3 H 2 0 ] , LiOM e and CO, 1 yields [R u(C O )2 ('S 2N 2 M e2')] 5. Spectroscopic data indicate that 5 and the parent com plex [R u(C O )2 ('S 2 N 2 H 2')] differ with respect to their core structures. Influence o f the am ine m ethylation on structure and reactivity o f com plexes with [M ('S 2N 2 R 2')] cores, R = H, M e, is discussed.