Formation and Redox Reactivity of Osmium(II) Thionitrosyl Complexes

Abstract

Reaction between [Os(VI)(tpm)(Cl)(2)(N)](PF(6)) (tpm = tris(1-pyrazolyl)methane) (1) or Os(VI)(Tp)(Cl)(2)(N) (Tp = hydrotris(1-pyrazolyl)borate anion) (2) and CS(2) + N(3)(-) in acetone gives the corresponding thionitrosyl complexes, (-)SCN, and N(2). There is an extensive reactivity chemistry of the thionitrosyl group in [Os(II)(tpm)(Cl)(2)(NS)](PF(6)) (3b). Reaction between 3b and PPh(3) occurs with S-atom transfer to give [Os(IV)(tpm)(Cl)(2)(NPPh(3))](+) and S=PPh(3). 3b undergoes chemical or electrochemical reduction to give the corresponding Os(II) ammine complex and H(2)S. O-atom transfer from O=NMe(3) to 3b occurs to give Os(III)(tpm)(Cl)(2)(NSO). Competitive NO(+)/NS(+) exchange and S(2)(-) transfer occur in the reaction between [Os(II)(tpm)(Cl)(2)(NS)](BF(4)) (3c) and NO(+) to give a mixture of [Os(VI)(tpm)(Cl)(2)(N)](+) and [Os(II)(tpm)(Cl)(2)(NO)](+).

Terminal Nitrido and Imido Complexes of the Late Transition Metals

“…In general, Os(VI) nitrido complexes are electrophilic (though organometallic nitrides are nucleophillic) [79] and react with various nucleophiles to form products with new bonds to the nitride nitrogen atom (Scheme 8). [80][81][82][83][84][85][86][87][88][89][90][91][92][93][94][95][96][97][98] The nitrido group in these Os compounds does not display significant nucleophilicity. In fact, Osnitrido species react with electrophilic acylating reagents via ligand substitution pathways that keep the OsN bond intact.…”

Ruthenium chalcogenonitrosyl and bridged nitrido complexes containing chelating sulfur and oxygen ligands

“…While nitrosyl complexes of transition metals are well documented, 1 the chemistry of the heavier chalcogen analogues, namely, thionitrosyl and selenonitrosyl complexes, has received less attention [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] due, in part, to the difficulty of their preparations. Common synthetic routes to thionitrosyl complexes include (a) sulfur atom transfer to metal nitrides, (b) reaction of N 3 S 3 Cl 3 or NS + salts with metal complexes, (c) halide abstraction from thiazyl complexes, and (d) reaction of S 4 N 4 with metal halides or nitrides.…”

16 The noble metals

“…The former is especially versatile and can be converted into an NH 3 complex by reduction, an NSO complex by reaction with Me 3 NO and an NPPh 3 complex with PPh 3 . 118 The crystal structure of [Os(2,2 H -bipy) 3 ] 2 [Cr(CN) 6 ]ClÁ8H 2 O and its ruthenium analogue have been reported. The complex anion partly quenches the luminescence of the cation, probably by involving the 2 T 2g state of the anion.…”