P-Phosphanylamino-phosphaalkenes were chosen as new hybrid ligands with the aim to combine the strong pi-accepting capacity of phosphaalkenes with the pattern of catalytically significant iminobisphosphines. The ligands (Me3Si)2C=PN(R)PPh2 (R = 1-Ada, tBu), available from iminophosphanides with P-chlorophosphaalkenes, were reacted with several metal precursors (Pt, Pd, Ni, Rh, Au). The 2:1 reactions with platinum dichloride are leading -in a curios way- to complexes where the chlorine atom have

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... migrated from platinum to the coordinated phosphaalkene phosphorus atoms (P-chloro-P-platina ylides). The addition of the chlorine ions to the phosphaalkene phosphorus atoms leads to a stereogenic centers (chiral phosphorus atoms), and the bischelate will display four steric arrangements: the cis/trans orientation of the ligands together with the syn or anti orientation of the chlorine atoms. From the 2:1 complexes of (Me3Si)2C=PN(1-Ada)PPh2 with PtCl2 three from the four possible isomers were crystallographically characterized. The reactions with Rh(CO)Cl(PPh3)2 gave rise to unique tetradentate dianionic phoshane/phosphanide Rh(III) complexes formed after unexpected elimination of one (SiMe3)2C unit from two of the phosphanylamino-phosphaalkene molecules. Further structure determinations include complexes of Pd(II), Ag(I), and Ni(0) with different coordination modes of the phosphanylamino-phosphaalkene ligands, and products from elimination, hydrogenation and hydrohalogenation reactions of the coordinated ligands.