Structural alternatives in R-2(Cl)P:GaCl3 systems (R = alkyl, phenyl), including examples of intermolecular P->P coordination
Structural alternatives in R-2(Cl)P:GaCl3 systems (R = alkyl, phenyl), including examples of intermolecular P->P coordination
复制标题
DOI：
10.1021/om9703595
复制
发表时间：
1997-10-14
期刊：
影响因子：
2.8
通讯作者：
Wu, G
中科院分区：
文献类型：
--
作者：
Burford, N;Cameron, TS;Wu, G
（二烷基/二芳基）氯膦-氯化镓反应混合物的系统NMR研究揭示了三种结构的替代物，它们通过溶液中的平衡而相关，并且它们的相对稳定性取决于取代基的性质（R = Me，Et，Pr-i，Bu-t，Ph）和反应化学计量。在所有情况下都观察到配位络合物R-2（Cl）P--> GaCl_3，并且衍生物（R = Pr_i）已经被晶体学表征。对于较小的R取代基（R = Me、Et、Pr 1、Ph），观察到二磷阳离子的四氯镓酸盐[R-2（Cl）P-PR 2]（+），这与先前的报道一致。固态P-31 CPMAS NMR光谱将甲基衍生物与新盐[Me-2（Cl）P-P（Me-2）GaCl 3][GaCl 4]区分开来，新盐含有膦-磷鎓-氯化镓阳离子，其已被晶体学表征。的结构的替代品的相对稳定性的因素进行了讨论，和R-2（Cl）P：GaCl 3的异构形式之间的比较。
Systematic NMR studies of (dialkyl/diaryl)chlorophosphine-gallium chloride reaction mixtures reveal three structural alternatives, which are related by equilibria in solution, and their relative stability is dependent on the nature of the substituent (R = Me, Et, Pr-i, Bu-t, Ph) and the reaction stoichiometry. The coordination complex R-2(Cl)P-->GaCl3 is observed in all cases, and a derivative (R = Pr-i) has been crystallographically characterized. Tetrachlorogallate salts of the diphosphorus cations [R-2(Cl)P-PR2](+) are observed for smaller R substituents (R = Me, Et, Pr-i, Ph), consistent with a previous report. Solid-state P-31 CPMAS NMR spectra distinguish the methyl derivative from the novel salt [Me-2(Cl)P-P(Me-2)GaCl3][GaCl4], containing a phosphine-phosphenium-gallium chloride cation, which has been crystallographically characterized. Factors governing the relative stabilities of the structural alternatives are discussed, and comparisons are made between the isomeric forms for R-2(Cl)P:GaCl3.