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Synthesis of New Mixed Phosphine∼Iminophosphorane Bidentate Ligands and Their Coordination to Group 10 Metal Centers

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posted on 14.03.2005, 00:00 by Leïla Boubekeur, Louis Ricard, Nicolas Mézailles, Pascal Le Floch
The selective monobromation of a symmetrical bidentate diphosphine (dppm = bis-diphenylphosphinomethane) yielding a highly reactive intermediate, 2 (P∼PBr+·Br-), is reported. Two methods of trapping were devised to produce mixed phosphine−aminophosphonium salts 3 (P∼PNHR+·Br-). The first method relies on the reaction of 2 with 2 equiv of primary amine to give 3ac (P∼PNHR+·Br-, R = p-Me-Bn, p-MeO-Bn, Ph). The second method utilizes 1 equiv of primary amine and DABCO as trapping agent to give 3ae (P∼PNHR+·Br-, R = p-Me-Bn, p-MeO-Bn, Ph, nBu, α(+)-Me-benzyl). These salts were then deprotonated quantitatively to yield the desired new phosphine−iminophosphorane ligands 4ae (P∼PNR). This simple strategy allows for a wide variation of the R substituent at the nitrogen donor group (R = alkyl, aryl, benzyl). In particular, the optically pure ligand 4e (R = α(+)-Me-benzyl) was obtained in one pot from commercially available α(+)-Me-benzylamine. Reaction of 4 with Pd(COD)Cl2 affords the complexes 5 via coordination to Pd(II) centers and revealed the chelating behavior of these ligands. X-ray crystal structures of 5a (presented in ESI), 5c, and 5e are reported. Complexes of platinum(II), 6c and 6e, were also synthesized and characterized crystallographically. The complex of nickel(II), 7a, adopts a tetrahedral geometry as shown by X-ray analysis and consistent with a lack of NMR signal.

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