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Reference

Synthesis and Electrochemical Properties of Transition Metal Complexes of 2,2':6',2''-Terpyridine 1,1''-Dioxide

Synthesis and Electrochemical Properties of Transition Metal Complexes of 2,2':6',2''-Terpyridine 1,1''-Dioxide. Ito, Kaname; Nagata, Toshi; Tanaka, Koji (Institute for Molecular Science and Department of Structural Molecular Science, CREST-Japan Science and Technology Corporation (JST) The Graduate University for Advanced Studies, Myodaiji Okazaki 444-8585, Japan). Inorganic Chemistry, 40(24), 6331-6333 (English) 2001 American Chemical Society. CODEN: INOCAJ. ISSN: 0020-1669. DOCUMENT TYPE: Journal CA Section: 78 (Inorganic Chemicals and Reactions) Section cross-reference(s): 72, 75 The synthesis and characterization of a series of first-row transition metal complexes of 2,2',6',2''-terpyridine 1,1''-dioxide (terpyO2) are reported. Four new bis complexes [M(terpyO2)]X2 (M = Mn, Fe, Co and Ni; X = ClO4 and BF4) and one mono complex [Cu(terpyO2)(H2O)](ClO4)2 were isolated and characterized, and electrochem. properties were examd.

Stepwise Synthesis of [Ru(trpy)(L)(X)]n+ (trpy = 2,2':6',2''-Terpyridine; L = 2,2'-Dipyridylamine; X = Cl-, H2O, NO2-, NO+, O2-)

Stepwise Synthesis of [Ru(trpy)(L)(X)]n+ (trpy = 2,2':6',2''-Terpyridine; L = 2,2'-Dipyridylamine; X = Cl-, H2O, NO2-, NO+, O2-). Crystal Structure, Spectral, Electron-Transfer, and Photophysical Aspects. Chanda, Nripen; Mobin, Shaikh M.; Puranik, Vedavati G.; Datta, Anindya; Niemeyer, Mark; Lahiri, Goutam Kumar (Department of Chemistry, Indian Institute of Technology Bombay, Mumbai 400076, India). Inorganic Chemistry, 43(3), 1056-1064 (English) 2004 American Chemical Society. CODEN: INOCAJ. ISSN: 0020-1669. DOCUMENT TYPE: Journal CA Section: 78 (Inorganic Chemicals and Reactions) Section cross-reference(s): 67, 72, 73, 75, 77 Ru-terpyridine complexes incorporating a 2,2'-dipyridylamine ancillary ligand [RuII(trpy)(L)(X)](ClO4)n [trpy = 2,2':6',2''-terpyridine; L = 2,2'-dipyridylamine; and X = Cl-, n = 1(1); X = H2O, n = 2(2); X = NO2-, n = 1(3); X = NO+, n = 3(4)] were synthesized in a stepwise manner starting from RuIII(trpy)(Cl)3. The single-crystal x-ray structures of all of the four members (1-4) were detd. The Ru(III)/Ru(II) couple of 1 and 3 appeared at 0.64 and 0.88 V vs. the SCE in MeCN. The aqua complex 2 exhibited a metal-based couple at 0.48 V in H2O, and the potential increased linearly with the decrease in pH. The electron-proton content of the redox process for pH's of 6.8-1.0 is a 2e-/1H+ process. However, the chem. oxidn. of 2 by an aq. Ce(IV) soln. in 1 N H2SO4 led to the formation of corresponding oxo species [RuIV(trpy)(L)(O)]2+ via the concerted 2e-/2H+ oxidn. process. The two successive redns. of the coordinated nitrosyl function of 4 appeared at +0.34 and -0.34 V corresponding to RuII-NO+ ? RuII-NO· and RuII-NO· ? RuII-NO-, resp. The 1-electron-reduced RuII-NO· species exhibited a free-radical ESR signal at g = 1.990 with N hyperfine structures at 77 K. The NO stretching frequency of 4 (1945 cm-1) was shifted to 1830 cm-1 in the case of [RuII(trpy)(L)(NO·)]2+. In aq. soln., the nitrosyl complex 4 slowly transformed to the nitro deriv. 3 with the pseudo-first-order rate const. of k298/s-1 = 1.7 ′ 10-4. The chloro complex 1 exhibited a dual luminescence at 650 and 715 nm with excited-state lifetimes of 6 and 1 ms, resp.