Transition metal complexes with sulfur ligands, 145. [Ru(NO)(' py(bu)S4 ')]Br, a complex with [Ru(NO)(NS4)] core, activated CH2 groups, and interionic interactions in the solid state (' py(bu)S(4)'(2-)=2,6-bis(2-mercapto-3,5-di-tert-butylphenylthio)dimethylpyridine(2-))

In the search for soluble and reactive ruthenium nitrosyl complexes [Ru(NO) ('py(bu)S(4)')]Br ([2]Br) was synthesized by template alkylation of NBu4[Ru (NO)(S-'bu(2)')(2)] with py(CH2Br)(2) ['py(bu)S(4)('2-)=2,6-bis(2-mercapto- 3,5-di-tert-butyl-phenylthio)dimethylpyridine(2-); S-tbu(2)'2- = 2-mercapto -3,5-di-tert-butylphenylthiolate(2-);py(CH2Br)(2) = 2,6-bis(bromomethyl)pyr idine]. The solid state structure of 2 has been determined by X-ray diffrac tion, which reveals a head-to-head O-O interaction between the linear Ru-NO entities. The ligand CH2 protons of [2](+) are activated and exchange with D+ under ambient conditions. The v(NO) band of [2]Br appears at 1841 cm(-1 ) in the solid state (KBr or hostaflon mull) and is significantly blue-shif ted in solution (1879 cm(-1) in MeOH, 1886 cm(-1) in DMF). A similar blue-s hift (1866 cm(-1) in KBr vs. 1888 cm(-1) in MeOH) has been found for [Ru(NO )('pyS(4)')]Br ([1]Br) which contains the parent [Ru(NO)('pyS(4)('))](+) ca tion ['pyS(4)('2-) = 2,6-bis(2-mercaptophenylthio)dimethylpyridine(2-)]. Th ese v(NO) shifts can be explained either by an interionic charge-transfer b etween the bromide anions and the nitrosyl complex cation or by O-O interac tions between two NO ligands as found for solid-state [2]Br. These interact ions are not found for [1]OTs which exhibits a v(NO) band at ca. 1890 cm(-1 ) in the solid state (KBr, hostaflon) as well as in MeOH solution.