Deoxygenation of the syn-3-phosphabicyclo[3.1.0]hexane 3-oxides bearing a 3-phenyl or a 3-(4-methylphenyl) substituent (1a,b) by trichlorosilane took place already at mild condition and resulted in the corresponding phosphines (2a,b) with retention of configuration at phosphorus, while in the case of 3-(2-methylphenyl)-3-phosphabicyclo[3.1.0]hexane (2c), the inversion of the phosphorus atom was observed in solution under ambient conditions that was evaluated by quantum chemical calculations. A further phosphine ligand (5) was obtained by the reduction of 4-dichloromethylene-1,4-dihydrophosphinine oxide (4). The phosphine ligands (2 and 5) were used in the preparation of Rh(III) complexes (3 and 6). A Pd(II) complex of type PdCl2(5)2(7) was also prepared. The stereostructures of a series of Rh(III) complexes of 3-aryl-3-phosphabicyclo[3.1.0]hexanes (3b-syn, 3c-syn and 3c-anti) were elucidated by single crystal X-ray analysis confirming the relative position of the dichlorocyclopropane and the P-substituent. © 2004 Elsevier B.V. All rights reserved.
Odinets, I. L., Vinogradova, N. M., Lyssenko, K. A., Golovanov, D. G., Petrovskii, P. V., Mastryukova, T. A., … Keglevich, G. (2005). Rhodium(III) and palladium(II) complexes of some P-heterocycles; synthesis and X-ray structures. Journal of Organometallic Chemistry, 690(3), 704–712. https://doi.org/10.1016/j.jorganchem.2004.08.051