N-Acetyl- N, N-dipyrid-2-yl (cyclooctadiene) rhodium (I) and iridium (I) complexes: Synthesis, X-ray structures, their use in hydroformylation and carbonyl hydrosilylation reactions and in the polymerization of diazocompounds

Abstract

The synthesis of novel N-acetyl- N, N-dipyrid-2-yl complexes of Rh I and Ir I, i.e. [RhCl(CH 3CONPy 2)(COD)] ( 1) and [IrCl(CH 3CONPy 2)(COD)] ( 2), respectively, is described. Upon prolonged treatment in CH 2Cl 2 at room temperature, complex 1 is transformed into a cationic Rh-complex, i.e. [Rh(CH 3CONPy 2)(COD) +RhCl 2(COD) −] ( 1a). Compound 1a crystallizes in the monoclinic space group P2 1/ c, complex 2 crystallizes in the triclinic space group P 1 ¯ . Compound 1 was investigated for its catalytic activity in the hydroformylation of cyclooctene as well as of 1-octene. In addition, 1 was used in various carbonyl hydrosilylation reactions of both aldehydes and ketones. There, turn-over numbers up to 50 000 and yields in the range of 85–100% were observed. Finally, compound 1 was successfully used for the polymerization of N 2CHCOOEt yielding highly stereoregular poly(ethoxycarbonylcarbene) with M w = 67 000 g/mol and a polydispersity index (PDI) of 2.59.