Axial ligand substitutions in trans-bis[1,2-phenylenebis(dimethylarsine)] complexes of ruthenium(II)

Abstract

The series of salts trans-[RuCl(pdma)2L]PF6[pdma = 1,2-phenylenebis(dimethylarsine); L = MeCN 1, pyridine (py)2, 1-methylmidazole (mim)3, benzonitrile 4, 4-ethylpyridine 5, dimethyl sulfoxide 6, pyrazine 7 or PPh38] were prepared by reaction of trans-[RuCl(pdma)2(NO)]2+ with 1 equivalent of NaN3 in acetone at room temperature followed by reflux with an excess of L in butan-2-one. Reaction of trans-[RuCl(pdma)2(NO)]2+ at room temperature in mim afforded the known complex trans-[RuCl(NO2)(pdma)2]. Methylation of 7 with MeI at room temperature gave trans-[RuCl(pdma)2(mpyz)][PF6]29(mpyz =N-methylpyrazinium cation). Treatment of 3 with an excess of NaN3 in refluxing mim–water afforded trans-[Ru(N3)(pdma)2-(mim)]PF610 which is converted into trans-[Ru(pdma)2(mim)2][PF6]211 by reaction with NO2BF4 in acetone at room temperature, followed by heating in mim. Single-crystal structures of trans-[RuCl(NO2)(pdma)2], trans-[RuCl(pdma)2(NO)][PF6]2, 2·dmf (dmf = dimethylformamide) and 11 have been determined.