Oxidant-Induced Hydride Abstraction from [Pt(μ-PBut2)(H)(PBut2H)]2 Yielding [Pt2(μ-PBut2)2(H)(PBut2H)2]C3(CN)5. Spectroscopic, Crystallographic, and Theoretical Comparison of the Structures of Two “Tautomers”
Oxidant-Induced Hydride Abstraction from [Pt(μ-PBut2)(H)(PBut2H)]2 Yielding [Pt2(μ-PBut2)2(H)(PBut2H)2]C3(CN)5. Spectroscopic, Crystallographic, and Theoretical Comparison of the Structures of Two “Tautomers”
复制标题
氧化剂诱导从 [Pt(μ-PBut2)(H)(PBut2H)]2 中提取氢化物，得到 [Pt2(μ-PBut2)2(H)(PBut2H)2]C3(CN)5。两种“互变异构体”的结构比较
DOI：
10.1021/ja980932r
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发表时间：
1998
影响因子：
15
通讯作者：
A. Albinati
中科院分区：
文献类型：
--
作者：
P. Leoni;M. Pasquali;A. Fortunelli;G. Germano;A. Albinati
铂(II)磷桥二氢化物[Pt(μ-PBut2)(H)(PBut2H)]2, 1在甲苯中与四氰乙烯(TCNE)反应生成电荷转移络合物1·TCNE，该络合物仅在固态下稳定。通过将 1·TCNE 溶解在极性溶剂中，电子转移迅速发生，随后失去一个氢配体并形成不饱和 Pt(II)Pt(II) 衍生物 [Pt2(μ-PBut2)2(H)(PBut2H)2]+TCNE-, 2a。 2a在空气中重结晶得到[Pt2(μ-PBut2)2(H)(PBut2H)2]+[C3(CN)5]-晶体，2b，其结构通过X射线衍射解析。当 1 与四氰基醌二甲烷 (TCNQ) 反应时，观察到相同类型的反应，形成类似的、结构特征明确的阳离子 2+ 的 TCNQ-盐。当 1 与等摩尔量的 [Cp2Fe]PF6 作为氧化剂（Cp = 环戊二烯基）反应时，可以更好地观察从 1 被取代的氢化配体所发生的情况。在这种情况下，我们分离出 (2)PF6, 2d 和 [Pt2(μ-PBut2)(μ-H)(PBut2H)3(H)]PF6, 3d 的 1:1 混合物，后者...
The platinum(II) phosphido-bridged dihydride [Pt(μ-PBut2)(H)(PBut2H)]2, 1, reacts with tetracyanoethylene (TCNE) in toluene to give the charge-transfer complex 1·TCNE, which is stable only in the solid state. By dissolving 1·TCNE in polar solvents, electron transfer occurs rapidly, followed by loss of one of the hydrido ligands and formation of the unsaturated Pt(II)Pt(II) derivative [Pt2(μ-PBut2)2(H)(PBut2H)2]+TCNE-, 2a. Recrystallization of 2a in the air gives crystals of [Pt2(μ-PBut2)2(H)(PBut2H)2]+ [C3(CN)5]-, 2b, whose structure was solved by X-ray diffraction. The same type of reaction was observed when 1 was reacted with tetracyanoquinodimethane (TCNQ), forming the analogous, structurally characterized, TCNQ- salt of cation 2+. What happened to the hydrido ligand displaced from 1 was better seen when 1 was reacted with an equimolar amount of [Cp2Fe]PF6 as the oxidant (Cp = cyclopentadienyl). In this case we isolated a 1:1 mixture of (2)PF6, 2d, and [Pt2(μ-PBut2)(μ-H)(PBut2H)3(H)]PF6, 3d, the latter...