Reactivity of Osmium(VI) Nitrides with the Azide Ion

Abstract

A variety of reactions occur between trans-[OsVI(tpy)(Cl)2(N)]+ (1) (tpy = 2,2‘:6‘,2‘‘-terpyridine) or [OsVI(tpm)(Cl)2(N)]+ (2) (tpm = tris(1-pyrazolyl)methane) and N3 -. The reaction between 2 and N3 - gives the stable dinitrogen complex OsII(tpm)(Cl)2(N2), but with 1 the chemistry is solvent dependent. One-electron reduction to give trans,trans-(tpy)(Cl)2OsII(N2)OsII(Cl)2(tpy) occurs in nonpolar solvents. 1 and 2 react with N3 - in the presence of CS2 to give the thionitrosyls [OsII(L3)(Cl)2(NS)]+ (L3 = tpy, tpm), -SCN, and N2. A reaction between 1 and excess N3 - in CH3CN occurs to give the first OsIII-5-CH3-tetrazolate complex, and it has been characterized by X-ray crystallography (structure shown).

Bioinspired control of colloidal silica in vitro by dual polymeric assemblies of zwitterionic phosphomethylated chitosan and polycations or polyanions

“…Since silica removal by dissolution is a challenge both from an environmental and safety perspective [68,69], commonly practiced control approaches have been limited to: (a) maintaining undersaturation (leading to water wastage), (b) pre-treatment (with high capital/equipment costs) and (c) inhibition of silica/silicate formation by chemical additives. The latter approach is practiced by some water service industries, with partial success [70]. Our on-going research efforts in the (bio)silicification area focus on the inhibitory effects of polymeric molecules on colloidal silica formation by studying the stabilization of silicic acid by these polymers [71][72][73][74][75][76][77][78].…”

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.…”

“…21 Selenonitrosyl complexes can be obtained from the reaction of metal nitrides with selenium. To date, [Os(NSe)TpCl 2 ] (Tp -= hydrotris(pyrazol-1-yl)borate) 10 and [Ir(NSe)(PNP)] + (PNP = N(CHCHPBu 2 t ) 2 ) 18 are the only isolated selenonitrosyl complexes that have been characterised by X-ray diffraction. To our knowledge, Ru selenonitrosyl complexes have not been reported.…”

“…Similar stretching frequencies have been found in reported thio-and selenonitrosyl complexes. 10,18 Both 1 and 2 have been characterised by X-ray diffraction. The molecular structures of 1 and 2 are shown in Figs 1 and 2, respectively.…”

Azide Chemistry – An Inorganic Perspective, Part II[‡][3+2]‐Cycloaddition Reactions of Metal Azides and Related Systems

“…[141,190] Complexes 64-66 decomposed with evolution of nitrogen to brown polymeric materials with an NCS-bridging group (IR) and a Pd/S ratio of ½, i.e. both S equivalents remained with the metal.…”