[Ni(P Me 2 N Ph 2 ) 2 ](BF 4 ) 2 as an Electrocatalyst for H 2 Production

A nickel(II) bis(diphosphine) complex, [Ni(P Me 2 N Ph 2 ) 2 ](BF 4 ) 2 (P Me 2 N Ph 2 = 1,5-diphenyl-3,7-dimethyl-1,5-diaza-3,7-diphosphacyclooctane), has been synthesized and characterized. This complex, which contains pendant amines in the diphosphine ligand, is an electrocatalyst for hydrogen production by proton reduction. Using [(DMF)H]OTf as the acid, a turnover frequency of 1,540 s –1 was obtained with no added water, and a turnover frequency of 6,700 s –1 was found with 1.0 M water added. Thermochemical studies show that the hydride donor ability of [HNi(P Me 2 N Ph 2 ) 2 ](BF 4 ) is Δ G ° H – = 54.0 kcal/mol, and we estimate a driving force for H 2 elimination of 13.8 kcal/mol. [Ni(P Me 2 N Ph 2 ) 2 ](BF 4 ) 2 is the fastest H 2 production catalyst in the [Ni(P R 2 N R ′ 2 ) 2 ](BF 4 ) 2 family of complexes.