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
. 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
Mw = 67 000 g/mol and a polydispersity index (PDI) of 2.59.