Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, XLIX [1]. Untersuchungen zur Chelat-assistierten oxidativen Addition einer C–Cl-Bindung an Rhodium(I)-KompIexe und reaktives Verhalten von Phospha-rhoda-cyclopentanen / Preparation and Properties of, and Reactions with Metal-Containing Heterocycles, XLIX [1]. Investigations on the Chelate Assisted Oxidative Addition of a C–Cl Bond to Rhodium Complexes and Reactive Behaviour of Phospharhodacyclopentanes

The complex L2Rh(CO)Cl (3b) is obtained by reaction of [μ-ClRh(CO)2)2 (1) with L = Cl-[CH2]3-P(C6H11)2 (2b) in benzene at 20 °C. 3b crystallizes in the triclinic space group P1 with Z = 1. On re fluxing 3 b in benzene an oxidative addition of one C-Cl bond to rhodium takes place to give the rhodacyclopentane derivative [xxx] (4b). Not only steric aspects of the ligands L and high electron density of the metal, but also free rotation about the Rh-P axis is important for the oxidative addition. Temperature dependent 31P{1H} NMR spectra of 3b between - 90 and 90 °C exhibit only one doublet in accordance with one rotameric form. Action of PMe3 on [xxx] (4a) [L - Cl-[CH:]; -P(C6HQ2 (2a)] results in the formation of the cyclic acyl compound [xxx] (5a).