title: 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, [Ru(VI)O2(Por)], with p-chloroaniline, trimethylamine, tert-butylamine, p-nitroaniline, and diphenylamine afforded bis(amine)ruthenium(II) porphyrins, [Ru(II)(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, [Ru(IV)(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 [Ru(II)(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 dichloromethane 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 [Ru(IV)(TTP)(NH-p-C6H4Cl)2 . CH2Cl2 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) A and 135.8(6) degrees, respectively.
authors.affiliation: Department of Chemistry, The University of Hong Kong, China.
authors.forename: J S
authors.initials: JS
authors.lastname: Huang
authors.forename: X R
authors.initials: XR
authors.lastname: Sun
authors.forename: S K
authors.initials: SK
authors.lastname: Leung
authors.forename: K K
authors.initials: KK
authors.lastname: Cheung
authors.forename: C M
authors.initials: CM
authors.lastname: Che
mesh_terms: D000588:Amines / Q000737:chemistry*; D003577:Cytochrome P-450 Enzyme System / Q000737:chemistry; D008665:Metalloporphyrins / Q000737:chemistry*; D010084:Oxidation-Reduction; D010105:Oxygenases / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry*; D013329:Structure-Activity Relationship
chemical_list: D000588:Amines; D008665:Metalloporphyrins; D012428:Ruthenium; D003577:Cytochrome P-450 Enzyme System; D010105:Oxygenases; C022626:secondary amine monooxygenase