Syntheses and Structures of Ruthenium(II) N,S‐Heterocyclic Carbene Diphosphine Complexes and their Catalytic Activity towards Transfer Hydrogenation

Phosphine exchange of [Ru^IIBr(MeCOO)(PPh₃)₂(3‐RBzTh)] (3‐RBzTh=3‐benzylbenzothiazol‐2‐ylidene) with a series of diphosphines (bis(diphenylphosphino)methane (dppm), 1,2‐bis(diphenylphosphino)ethylene (dppv), 1,1′‐bis(diphenylphosphino)ferrocene (dppf), 1,4‐bis(diphenylphosphino)butane (dppb), and 1,3‐(diphenylphosphino)propane (dppp)) gave mononuclear and neutral octahedral complexes [RuBr(MeCOO)(η²‐P₂)(3‐RBzTh)] (P₂=dppm ( 2 ), dppv ( 3 ), dppf ( 4 ), dppb ( 5 ), or dppp ( 6 )), the coordination spheres of which contained four different ligands, namely, a chelating diphosphine, carboxylate, N,S‐heterocyclic carbene (NSHC), and a bromide. Two geometric isomers of 6 ( 6a and 6 b ) have been isolated. The structures of these products, which have been elucidated by single‐crystal X‐ray crystallography, show two structural types, I and II, depending on the relative dispositions of the ligands. Type I structures contain a carbenic carbon atom trans to the oxygen atom, whereas two phosphorus atoms are trans to bromine and oxygen atoms. The type II system comprises a carbene carbon atom trans to one of the phosphorus atoms, whereas the other phosphorus is trans to the oxygen atom, with the bromine trans to the remaining oxygen atom. Complexes 2 , 3 , 4 , and 6a belong to type I, whereas 5 and 6 b are of type II. The kinetic product 6 b eventually converts into 6a upon standing. These complexes are active towards catalytic reduction of para‐methyl acetophenone by 2‐propanol at 82 °C under 1 % catalyst load giving the corresponding alcohols. The dppm complex 2 shows the good yields (91–97 %) towards selected ketones.