RUTHENATE(VI)-CATALYZED DEHYDROGENATION OF PRIMARY AMINES TO NITRILES, AND CRYSTAL-STRUCTURES OF U(BIPY)(2)(NH2CH2PH)(2)][PF6](2)CENTER-DOT-0.5MEOH AND IS-[RU(BIPY)(2)(NCPH)(2)][PF6](2)CENTER-DOT-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)(NH2CH2P h)(2)](2+) and the new cis-[Ru(bipy)(2)(NH2CH2R)(2)](2+) (R = o-, m- o r 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 ruthen ium complexes to the corresponding nitriles in cis-[Ru(L-L)(2)(NCR)(2) ](2+) (L-L = bipy or phen) by peroxodisulfate demonstrated. The crysta l 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-ordin ated 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.