Departamento de Química Orgánica e Inorgánica, Facultad de Química, Universidad de Oviedo, 33071, Oviedo, Spain.
Dalton Trans. 2009 Nov 14(42):9280-90. doi: 10.1039/b903375k. Epub 2009 Oct 2.
Diphosphinoketenimine ligands (PPh(2))(2)C=C=NR (1a R = (t)Bu, 1b R = Ph) were reacted with different Cu(I), Ag(I), Au(I), Pd(II), Ru(II) and Mo(0) metal complexes bearing weakly coordinating ligands yielding a number of mono-, di-, and trimetallic species with the diphosphine acting as either chelate or bridging ligand. The reactivity of some of the new complexes toward water and MeLi was investigated. The mononuclear Pd(II) complex [PdCl(2){(PPh(2))(2)C=C=NPh}] (6b) is transformed into the diphosphinoamide complex [PdCl(2){(PPh(2))(2)CHC(=O)(NHPh)}] (12) by nucleophilic addition of water. Similarly, treatment of 6b with MeLi yields the diphosphinoenamine complex [PdCl(2){(PPh(2))(2)C=C(Me)(NHPh)}] (14). A different behaviour is observed in the treatment of diphosphinoketenimine with water in the presence of Cu(I) ion, which leads to hydrolysis of the ligand involving P-C bond cleavage, underscoring the influence of the coordination environment in the reactivity showed by the coordinated ligand. The liberation of the metal assisted synthesized diphosphines from the Pd(II) metal center can be achieved easily and in quantitative yields by treatment with aqueous KCN solution.
二膦烯亚胺配体（PPh(2))(2)C=C=NR（1a R = (t)Bu, 1b R = Ph）与不同的 Cu(I)、Ag(I)、Au(I)、Pd(II)、Ru(II)和 Mo(0)金属配合物反应，这些金属配合物带有弱配位配体，生成了一系列单核、二核和三核配合物，其中二膦配体作为螯合或桥联配体。研究了一些新配合物对水和 MeLi 的反应性。单核 Pd(II)配合物 [PdCl(2){(PPh(2))(2)C=C=NPh}]（6b）通过水的亲核加成转化为二膦酰胺配合物 [PdCl(2){(PPh(2))(2)CHC(=O)(NHPh)}]（12）。同样，用 MeLi 处理 6b 得到二膦烯胺配合物 [PdCl(2){(PPh(2))(2)C=C(Me)(NHPh)}]（14）。在 Cu(I)离子存在下，二膦烯亚胺与水的反应表现出不同的行为，导致配体水解，涉及 P-C 键断裂，这突出了配位环境对配位配体反应性的影响。通过用 KCN 水溶液处理，可以从 Pd(II)金属中心轻松且定量地释放出金属辅助合成的二膦配体。
