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DOI: 10.1039/A804071K (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 2819-2826

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[hair space]†

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William P. Griffith, Bharti Reddy, Abdel G. F. Shoair, Maria Suriaatmaja, Andrew J. P. White and David J. Williams

Abstract

Catalytic dehydrogenation of benzylic and other primary amines RCH2NH2 to the corresponding nitriles RCN by the system trans-[Ru(OH)2O3]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-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][PF6]·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.

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