Rhodium(I) carbonyl complexes of ether‐phosphine ligands and their reactivity

Abstract

Abstract The reactions of dimeric complex [Rh(CO) 2 Cl] 2 with hemilabile ether‐phosphine ligands Ph 2 P(CH 2 ) n OR [ n = 1, R = CH 3 (a); n = 2, R = C 2 H 5 (b)] yield cis ‐[Rh(CO) 2 Cl(P ∼ O)] (1) [P ∼ O = η 1 ‐(P) coordinated]. Halide abstraction reactions of 1 with AgClO 4 produce cis ‐[Rh(CO) 2 (P ∩ O)]ClO 4 (2) [P ∩ O = η 2 ‐(P,O)chelated]. Oxidative addition reactions of 1 with CH 3 I and I 2 give rhodium(III) complexes [Rh(CO)(COCH 3 )ClI(P ∩ O)] (3) and [Rh(CO)ClI 2 (P ∩ O)] (4) respectively. The complexes have been characterized by elemental analyses, IR, 1 H, 13 C and 31 P NMR spectroscopy. The catalytic activity of 1 for carbonylation of methanol is higher than that of the well‐known [Rh(CO) 2 I 2 ] − species. Copyright © 2002 John Wiley & Sons, Ltd.