Synthesis and Structures of Palladium and Platinum A-Frame Complexes Bridged by a Novel Binucleating Ligand, N,N‘-Bis[(2-diphenylphosphino)phenyl]- formamidine
Synthesis and Structures of Palladium and Platinum A-Frame Complexes Bridged by a Novel Binucleating Ligand, N,N‘-Bis[(2-diphenylphosphino)phenyl]- formamidine
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DOI：
10.1021/om020003f
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发表时间：
2002-05
期刊：
影响因子：
2.8
通讯作者：
Naofumi Tsukada;O. Tamura;Y. Inoue
中科院分区：
文献类型：
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作者：
Naofumi Tsukada;O. Tamura;Y. Inoue
制备了一种新型双核配体N，N′-双[（2-二苯基膦）苯基]甲脒（Hdpfam），并将其用于合成同、杂双金属钯/铂配合物M2R2(μ-X)(μ-dpfam) （M = Pd, Pt; R = Me, p-Tol, Cl; X = Cl, Br， I; dpfam = N，N′-双[（2-二苯基膦）苯基]甲脒）。用2等量的MRX（tmeda）或MRX（cod）在tmeda存在下治疗Hdpfam产生同双金属配合物。以PtMe2（cod）和Hdpfam为原料，PdMeCl（cod）与PtMe（dpfam）反应得到了杂双金属配合物PdPtMe2(μ-Cl)（μ-dpfam）。用x射线分析方法测定了Pd2Cl2(μ-Cl)（μ-dpfam）和Pt2Me2(μ-Cl)（μ-dpfam）的晶体结构。结果表明，这两种配合物均具有P−M−Cl−M−P a -框架结构，其中每个金属中心具有轻微扭曲的方形平面几何形状，非桥接的σ-给体（Cl或Me）和μ-Cl呈顺式取向。用NaBH4处理Pt2Me2(μ-Cl)(μ-dpfam)，得到氢化物-溴化反应。
A novel binucleating ligand, N,N‘-bis[(2-diphenylphosphino)phenyl]formamidine (Hdpfam), has been prepared and utilized for the synthesis of homo- and heterobimetallic palladium/platinum complexes M2R2(μ-X)(μ-dpfam) (M = Pd, Pt; R = Me, p-Tol, Cl; X = Cl, Br, I; dpfam = N,N‘-bis[(2-diphenylphosphino)phenyl]formamidinate). Treatment of Hdpfam with 2 equiv of MRX(tmeda) or MRX(cod) in the presence of tmeda produced the homobimetallic complexes. The heterobimetallic complex PdPtMe2(μ-Cl)(μ-dpfam) was obtained by the reaction of PdMeCl(cod) with PtMe(dpfam), which was produced from PtMe2(cod) and Hdpfam. The crystal structures of Pd2Cl2(μ-Cl)(μ-dpfam) and Pt2Me2(μ-Cl)(μ-dpfam) have been determined by X-ray analysis. The results indicate that both complexes have P−M−Cl−M−P A-frame structures, in which each metal center has a slightly distorted square-planar geometry and the nonbridging σ-donor ligands (Cl or Me) and μ-Cl are in a cis orientation. Treatment of Pt2Me2(μ-Cl)(μ-dpfam) with NaBH4 gave the hydride-br...