[Cr(pincer2−)]2 as an electron shuttle for reductively promoted hydrazine disproportionation

Abstract

We describe here delivery of hydrazine to a reducing, low oxidation state chromium bound to a proton responsive ligand which has already been deprotonated. Reaction of PhHNNH₂ at a 4 : 1 mole ratio with the bis-(pyrazolate)pyridyl pincer ligated reducing agent [Cr^IIL]₂ gives prompt conversion to [Cr^III₂L₂(PhNH₂)₂(μ-PhHNN)], with release of NH₃ and C₆H₆, a new disproportionation of the hydrazine, with trapping of PhHNN as its dianion, bridging the two chromium centers. The redox balance of the reaction is discussed, and participation by Brønsted basic sites on the bis-(pyrazolate)pyridyl pincer ligand L²⁻ is suggested, but no hydrazine protons remain on the pincer in the product.