PH‐Functionalized Phosphenium Complexes [C5R5(OC)2 WP(H)R′] (R′ = tBu, sMes): Synthesis, Isomerization, and Transformation into Hydrido Complexes Containing a tBuP(H)OH Ligand
PH‐Functionalized Phosphenium Complexes [C5R5(OC)2 WP(H)R′] (R′ = tBu, sMes): Synthesis, Isomerization, and Transformation into Hydrido Complexes Containing a tBuP(H)OH Ligand
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PH 官能化磷络合物 [C5R5(OC)2 WP(H)R′] (R′ = tBu, sMes)：合成、异构化和转化为含有 tBuP(H)OH 配体的氢化物络合物
DOI：
10.1002/anie.199525001
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发表时间：
1995
影响因子：
--
通讯作者：
U. Weis
中科院分区：
文献类型：
--
作者：
W. Malisch;U. Hirth;K. Grün;M. Schmeusser;Oliver Fey;U. Weis
[Cp (OC), M= PR,](M= Mo, W) 类型的鏻配合物中的金属-磷双键越来越多地用于环加成反应，[']这代表了这些化合物在金属配合物介导的有机磷化合物合成中的应用的第一步。然而，在迄今为止已知的化合物中，磷上的大体积有机或杂原子取代基可稳定双键，相当大地限制了 M= P 单元的加成活性。['] 在这种情况下，有希望的候选者是具有 sp2 杂化磷原子的氢取代的 M= P 单元，它可以被视为初级卡宾配合物的磷类似物。['"* b1 这些单元显示出增加的环加成潜力，但氢迁移引起异构化的可能性必须此外，还必须考虑涉及高反应性 P-H 键的交换和插入反应的可能性。这些 R (H) P= M 配合物的存在，已被反复假定为 PH- 反应的中间体。
The metal-phosphorus double bond in phosphenium complexes of the type [Cp (OC), M= PR,](M= Mo, W) is employed increasingly in cycloaddition reactions,['] which represent a first step towards the application of these compounds in the synthesis of organophosphorus compounds mediated by metal complexes. However, in the compounds known to date, bulky organo or heteroatom substituents on the phosphorus, which stabilize the double bond, limit the addition activity of the M= P unit quite considerably.['] In this context promising candidates are hydrogen-substituted M= P units with an sp2-hybridized phosphorus atom, which can be regarded as phosphorus analogues of primary carbene complexes.['"* b1 These units display increased potential for cycloaddition, but the possibility of isomerizations by hydrogen migration must also be taken into account. Izcl Fur-thermore, the possibility of exchange and insertion reactions involving the highly reactive P-H bond must be con~ idered.'~'The existence of these R (H) P= M complexes, which have been postulated repeatedly as intermediates in reactions of PH-