Ruthenate(VI)-catalysed dehydrogenation of primary amines to nitriles, and crystal structures of cis-[Ru(bipy)2(NH2CH2Ph)2][PF 6]2·0.5MeOH and cis-[Ru(bipy)2(NCPh)2][PF6] 2·CH2Cl2

Catalytic dehydrogenation of benzylic and other primary amines RCH2NH2 to the corresponding nitriles RCN by the system trans-[Ru(OH)2O3]2-/S2O 82- has been investigated. The complex cis-[Ru(bipy)2(NH2CH2Ph)2] 2+ and the new cis-[Ru(bipy)2(NH2CH2R)2] 2+ (R = o-, m- or p-ClC6H4, o-MeC6H4, o- or p-MeOC6H4); cis-[Ru(phen)2(NH2CH2R)2] 2+ (R = Ph or p-MeOC6H4) and cis-[Os(bipy)2(NH2CH2Ph)2] 2+ have been made, and dehydrogenation of the co-ordinated amine in the ruthenium complexes to the corresponding nitriles in cis-[Ru(L-L)2(NCR)2]2+ (L-L = bipy or phen) by peroxodisulfate demonstrated. The crystal structures of cis-[Ru(bipy)2(NH2CH2Ph)2][PF 6]·0.5MeOH and cis-[Ru(bipy)2(NCPh)2][PF6] 2·CH2Cl2, the latter a product of co-ordinated amine dehydrogenation by peroxodisulfate to give cis-[Ru(bipy)2(NH2CH2Ph)2] 2+, were determined. Raman, infrared and 1H NMR data for the complexes have been measured; the latter suggest that the cis configurations of the amine complexes are retained in solution.