C. Che, Kwok‐yin Wong, C. Poon
May 21, 1986
Citations
0
Influential Citations
36
Citations
Journal
Inorganic Chemistry
Abstract
1,4,8,12-Tetramethyl-1,4,8,12-tetraazacyclopentadecane (15-TMC) was synthesized by the reaction of 1,4,8,12-tetraazacyclopentadecane with formaldehyde. Reactions of K/sub 2/(RuCl/sub 5/H/sub 2/O) with 15-TMC and 16-TMC (16-TMC = 1,5,9,13-tetramethyl-1,5,9,13-tetraazacyclohexadecane) in ethanol yielded trans-(RuLCl/sub 2/)Cl (L = 15-TMC and 16-TMC, respectively) in high yields. The syntheses of trans-(RuLBr/sub 2/)ClO/sub 4/ (L = (TMEA)/sub 2/ (TMEA = N,N,N',N'-tetramethyl-1,2-ethanediamine), 14-TMC (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), and 15-TMC), trans-(Ru(TMEA)/sub 2/(NCS)/sub 2/)NCS, and trans-(Ru(14-TMC)(CH/sub 3/CN)/sub 2/)(ClO/sub 4/)/sub 2/ are also described. The electrochemistry of trans-(RuLX/sub 2/)/sup +/ (L = (TMEA)/sub 2/, 14-TMC, 15-TMC, and 16-TMC; X = Cl, Br, and NCO) in acetonitrile were examined. Controlled-potential electrolyses of trans-(RuLX/sub 2/)/sup +/ at 1.30 V vs. the ferrocene couple generated some novel trans-(Ru/sup IV/LX/sub 2/)/sup 2 +/ complexes. The ligand-to-metal charge-transfer transitions in the UV-vis spectra of trans-(Ru/sup IV/(TMEA)/sub 2/X/sub 2/)/sup 2 +/ have been identified at 410 (X = Cl) and 570 nm (X = Br), which are considerably red-shifted with respect to their Ru(III) counterparts.