Stabilization of transition-metal complexes in high oxidation states by macrocyclic tertiary amines. Electrochemical generation and spectroscopic properties of novel dihalogeno and pseudohalogeno tetraamine complexes of ruthenium(IV)
Journal Article
·
· Inorg. Chem.; (United States)
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.
- Research Organization:
- Univ. of Hong Kong
- OSTI ID:
- 5532809
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 25:11; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
Similar Records
Monooxo complexes of ruthenium(V) as homogeneous redox catalysts for the electrooxidation of benzyl alcohol
Proton-coupled electron-transfer reactions. Mechanisms of two-electron reduction of trans-dioxoruthenium(VI) to trans-aquooxoruthenium(VI) and disproportionation of trans-dioxoruthenium(V)
Structural and electron self-exchange rate variations in isomeric (hexaamine)cobalt(III/II) complexes
Journal Article
·
Tue Mar 10 23:00:00 EST 1987
· Inorg. Chem.; (United States)
·
OSTI ID:6819778
Proton-coupled electron-transfer reactions. Mechanisms of two-electron reduction of trans-dioxoruthenium(VI) to trans-aquooxoruthenium(VI) and disproportionation of trans-dioxoruthenium(V)
Journal Article
·
Wed Jun 20 00:00:00 EDT 1990
· Journal of the American Chemical Society; (USA)
·
OSTI ID:6620125
Structural and electron self-exchange rate variations in isomeric (hexaamine)cobalt(III/II) complexes
Journal Article
·
Wed May 21 00:00:00 EDT 1997
· Inorganic Chemistry
·
OSTI ID:563609
Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400400 -- Electrochemistry
ABSORPTION SPECTRA
ABSORPTION SPECTROSCOPY
AMINES
BROMINE COMPLEXES
CATALYSTS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CHEMISTRY
CHLORINE COMPLEXES
COMPLEXES
DATA
ELECTROCHEMISTRY
ELECTRON TRANSFER
EXPERIMENTAL DATA
INFORMATION
LIGANDS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDATION
REDUCTION
RUTHENIUM COMPLEXES
SPECTRA
SPECTROSCOPY
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
VALENCE
VOLTAMETRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400400 -- Electrochemistry
ABSORPTION SPECTRA
ABSORPTION SPECTROSCOPY
AMINES
BROMINE COMPLEXES
CATALYSTS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CHEMISTRY
CHLORINE COMPLEXES
COMPLEXES
DATA
ELECTROCHEMISTRY
ELECTRON TRANSFER
EXPERIMENTAL DATA
INFORMATION
LIGANDS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDATION
REDUCTION
RUTHENIUM COMPLEXES
SPECTRA
SPECTROSCOPY
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
VALENCE
VOLTAMETRY