Synthesis and Characterization of the First Compounds Containing a Stable Phosphirenyl Cation: Crystal and Molecular Structure of [Ni(η3-PC2tBu2)(η5-P3C2tBu2)W(CO)5]†
Synthesis and Characterization of the First Compounds Containing a Stable Phosphirenyl Cation: Crystal and Molecular Structure of [Ni(η3-PC2tBu2)(η5-P3C2tBu2)W(CO)5]†
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第一个含有稳定磷膦基阳离子的化合物的合成和表征：[Ni(η3-PC2tBu2)(η5-P3C2tBu2)W(CO)5]†的晶体和分子结构
DOI：
10.1002/anie.199423301
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发表时间：
1994
影响因子：
--
通讯作者：
David M. Vickers
中科院分区：
文献类型：
--
作者：
A. G. Avent;F. Cloke;K. R. Flower;P. Hitchcock;J. Nixon;David M. Vickers
膦基阳离子（PC，tBu，）+作为配体，来自1）其特征质谱，其在m/z= 458处显示出母离子，显示出典型的同位素模式，并且峰与预期的裂解一致，在m/z= 320处的最强峰对应于从母化合物中失去tBuC= CtBu，和2）来自其1H、1 P = 1H}和13 C（1H）NMR光谱，特别是。在13 C NMR光谱中δ = 178.9处的多重峰，其作为AMXY自旋系统的A部分（表1）进行分析，并且是P3 C2部分的环碳的特征。31 P 1H NMR谱分析为AB，X自旋系统，AB，部分归属于P，C，环。由于1H和13 C（1H）NMR谱确定了两个化学上等价的CtBu片段，因此证实了三元PC 1环的存在。特别重要的是在三元环中的Px共振的化学位移，这非常接近于观察到的充分表征的，结构相关的配合物[Ni（q3-P3）（q 5-CH，tBu，）]。1951年
phosphirenyl cation (PC, tBu,)+ as ligand, from 1) its characteristic mass spectrum, which exhibits a parent ion at m/z= 458 showing the typical isotopic pattern, and peaks consistent with the expected fragmentation, the strongest peak at m/z= 320 corresponding to the loss of tBuC= CtBu from the parent compound, and 2) from its' H,'lP {'H}, and 13C {1H) NMR spectra, in particular. the multiplet at 6= 178.9 in the I3C NMR spectrum which analyses as the A part of an AMXY spin system (Table 1) and is characteristic of the ring carbon of the P3C2 moiety. The 31P {'H} NMR spectrum analyses as an AB, X spin system, the AB, part being assigned to the P, C, ring. Since the'H and 13C {1H] NMR spectra establish two chemically equivalent CtBu fragments, the presence of the three-membered PC, ring is confirmed. Of special significance is the chemical shift of the Px resonance in the three-membered ring, which lies very close to that observed for the fully characterized, structurally related complex [Ni (q3-P3)(q 5-C H, tBu,)].['51