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.
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