A series of RhI complexes was prepared and characterised with the following hemilabile amphiphilic phosphanes: R-(C6H 4)-(OCH2CH2)n-PPh2 [1 (R = tert-octyl, n = 1), 2 (R = tert-octyl, n̄ = 5), 3 (R = tert-octyl, n̄ = 13), 4 (R = n-nonyl, n̄ = 1.4), 5 (R = n-nonyl, n̄ = 5), 6 (R = n-nonyl, n̄ = 11)]. The reactions between 1-6 and [Rh(COD)(THF) 2]+, and the subsequent reaction with CO were studied by 31P NMR and IR spectroscopy. The data are consistent with the formation of P-coordinated and chelated (P,O) species for ligands 2-6, in agreement with the hemilabile character of these ligands. In the case of ligand 1, the complex trans-[Rh(1)2(CO)2]+ has been isolated and the cis-[Rh(1)2(CO)2]+ compound has been detected. [Rh(1)2(CO)]+ was prepared by decarbonylation of trans-[Rh(1)2(CO)2]+, and low-temperature NMR spectroscopic studies have shown the hemilabile character of 1 with a very weak P-O interaction. The molecular structure of trans-Rh(CO)(1)2Cl was determined by X-ray crystallography and shows that the conformation of the tert-octylphenoxyethyl chains is nearly identical to that previously reported in the complex trans-PdCl2(1) 2. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
|Journal||European Journal of Inorganic Chemistry|
|Publication status||Published - 18 Aug 2003|
- Hemilabile ligands