Parallel coordination of hydrazine to diruthenium units: synthesis and molecular structure of the cationic complexes [( η6-C 6Me 6) 2Ru 2( μ2-H) 2( μ2- η1, η1-H 2NNH 2)] 2+ and [( η6-C 6Me 6) 2Ru 2( μ2-H)( μ2- η1, η1-H 2NNH 2)( μ2-NH 2)] 2+

Abstract

The dinuclear cation [( η 6-C 6Me 6) 2Ru 2( μ 2-H) 3] + ( 1) reacts in aqueous solution with hydrazine to give the dicationic complexes [( η 6-C 6Me 6) 2Ru 2( μ 2-H) 2( μ 2- η 1, η 1-H 2NNH 2)] 2+ ( 2) and [( η 6-C 6Me 6) 2Ru 2( μ 2-H)( μ 2- η 1, η 1-H 2NNH 2)( μ 2-NH 2)] 2+ ( 3). The single-crystal X-ray structure analyses of 2 (tosylate salt) and 3 (triflate salt) reveal both complexes to contain an intact hydrazine ligand coordinated parallel ( μ 2- η 1, η 1) to the diruthenium backbone, comprising a RuRu double bond (2.69 Å) in 2 and a Ru–Ru single bond (2.85 Å) in 3. A single crystal of the mixed sulfate-hexafluorophosphate salt of [( η 6-C 6Me 6) 2Ru 2( μ 2-H)( μ 2- η 1, η 1-H 2NNH 2)( μ 2-N 2H 3)] 2+ ( 4), isolated from the mother liquor of 2, suggests this hydrazido complex to be an intermediate in the reaction from 2 to 3.