Reactivity of dioxoruthenium(VI) porphyrins toward amines. Synthesis and characterization of bis(arylamine)ruthenium(II), bis(arylamido)-and bis(diphenylamido)ruthenium(IV), and oxo(tert-butylimido)ruthenium(VI) porphyrins

Abstract

Reactions of dioxoruthenium(VI) porphyrins, [RuVIO2(Por)], with p-chloroaniline, trimethylamine, tert-butylamine, p-nitroaniline, and diphenylamine afforded bis(amine)ruthenium(II) porphyrins, [RuII(Por)(L)2] (L = p-ClC6H4NH2, Me3N, Por = TTP, 4-Cl-TPP; L = tBuNH2, Por = TPP, 3,4,5-MeO-TPP, TTP, 4-Cl-TPP, 3,5-Cl-TPP) and bis(amido)ruthenium(IV) porphyrins, [RuIV(Por)(X)2] (X = p-NO2C6H4NH, Por = TTP, 4-Cl-TPP; X = Ph2N, Por = 3,4,5-MeO-TPP, 3,5-Cl-TPP), respectively. Oxidative deprotonation of [RuII(Por)(NH2-p-C6H4Cl) 2] in chloroform by air generated bis-(arylamido)ruthenium(IV) porphyrins, [RuIV(Por)(NH-p-C6H4Cl)2] (Por = TTP, 4-Cl-TPP). Oxidation of [RuII(Por)-(NH2tBu)2] by bromine in dichloro-methane in the presence of tert-butylamine and traces of water produced oxo(imido)ruthenium(VI) porphyrins, [RuVI-O(Por)(NtBu)] (Por = TPP, 3,4,5-MeO-TPP, TTP, 4-Cl-TPP, 3,5-Cl-TPP). These new classes of ruthenium complexes were characterized by 1H NMR, IR, and UV/visible spectroscopy, mass spectrometry, and elemental analysis. The structure of [RuIV(TTP)(NH-p-C6H4Cl)2] · 2CH2Cl2 was determined by X-ray crystallography. The Ru - N bond length and the Ru-N-C angle of the Ru-NHAr moiety are 1.956(7) Å and 135.8(6)°, respectively.