Ammine and amido complexes of rhodium: Synthesis, application and contributions to analytics

Rhodium complexes resulting from the reaction of ammonia and rhodium diphosphine (PP) precursors have been investigated. A variety of ammine complexes of the type [Rh(PP)(NH3)(2)](+) has been synthesized and characterized by multinuclear NMR spectroscopy and X-ray crystallography. The possibility to use this complex type in hydrogenation reactions by acid activation was investigated. Furthermore the formation of dinuclear amido complexes [Rh(mu(2)-NH2)(PP)](2) (PP = dipamp, dppe, dppp, binap, diop) was observed when sodium amide was added to solvate complexes [Rh(PP)(solvent)(2)](+). These amido complexes could also be generated by the reaction of gaseous ammonia with rhodium complexes containing basic groups (OH- and OMe-) via N-H bond cleavage at room temperature and atmospheric pressure. (C) 2020 The Authors. Published by Elsevier B.V.