Halogeno ligand-substitution reactions of trihalogenoruthenium(III) complexes bearing ethylbis(2-pyridylmethyl)amine (ebpma), fac-[Ru III X 3 (ebpma)] (X = Cl; [1 Cl ], Br; [1 Br ]) were investigated to derive various complexes of desired properties and reactivities. The number of substitution of halogeno ligand (n) was controlled. Through the reaction of [1 Cl ] with sulfuric acid in acetonitrile, a mono-substituted acetonitrileruthenium(III) complex fac-[Ru III Cl 2 (NCCH 3 )(ebpma)] + (n = 1, [2] + ) was obtained, while the one-electron reduction reactions [a] 4040 Scheme 1. Synthetic strategy for chlorido substitution reactions (n; the number of dissociated and substituted chlorido of [1 Cl ]).
Nitrosylruthenium complexes bearing two 2,2'-bipyridine (bpy) or 2-pyridinecarboxylate (pyc) ligands, [Ru(NO)X(bpy) ] (X=CH CN, CH =CHCN, H O, Cl, ONO ) and [Ru(NO)(OH )(pyc) ] , were used as catalysts for the polymerization of acrylonitrile in N,N-dimethylformamide (DMF) under air without initiators to obtain polyacrylonitrile (PAN) with a high molecular weight and a narrow molecular weight distribution.
Four-electron oxidation of two anilines coordinated to a ruthenium(ii) center in a cis-form affords N1-phenylcyclohexa-3,5-diene-1,2-diimine through an N–C bond formation with N–H and C–H bond activation.
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