Ruthenate(VI)-catalysed Dehydrogenation of Primary Amines to Nitriles, and Crystal Structures of Cis-[Ru(bipy)2(nh2ch2ph)2][pf6]2·0.5meoh and Cis-[Ru(bipy)2(ncph)2][pf6]2·ch2cl2 †

Catalytic dehydrogenation of benzylic and other primary amines RCH2NH, to the corresponding nitriles RCN by the system trans-[Ru(OH)(2)O-3](2-)/S2O82- 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-CIC6H4, 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)][PF6].0.5 MeOH 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 H-1 NMR data for the complexes have been measured; the latter suggest that the cis configurations of the amine complexes are retained in solution.