Synthesis and Spectroscopic and X-ray Structural Characterization of Compounds Involving Boron-Phosphorus Multiple Bonds: Lithium Salts of Boryl Phosphides and Their Precursors
Synthesis and Spectroscopic and X-ray Structural Characterization of Compounds Involving Boron-Phosphorus Multiple Bonds: Lithium Salts of Boryl Phosphides and Their Precursors
复制标题
硼磷多重键化合物的合成、光谱和X射线结构表征：磷化硼的锂盐及其前体
DOI：
10.1021/ja00186a023
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发表时间：
1989
影响因子：
15
通讯作者：
P. Power
中科院分区：
文献类型：
--
作者：
R. A. Bartlett;H. V. Rasika Dias;X. Feng;P. Power
本文介绍了几种磷化硼锂盐及其前驱体的合成、光谱和结构表征。用R2 BX处理伯膦H2 PR '的锂盐（X= F，Cl）得到膦基硼烷（硼基膦）R2 BPHR '（R/R '= Ph/r-Bu（1）、Mes/r-Bu（2）、Trip/r-Bu（3）、Mes/Ph（4）、Mes/Cy（5）、Mes/Mes（6））（Mes= 2，4，6-Me_3C_6H_2，Trip= 2，4，6-α-Pr_3C_6H_2，Cy=环己基））。化合物1-6与1当量的n-BuLi或t-BuLi的反应提供了它们相应的锂盐[Li（Et 2 O）2 PR·BR 2]（7-12）。将2当量的12-冠-4添加到Li（Et 2 O）2 PR 'BMes 2（R'= Ph（10），Cy（11），Mes（12））中，得到溶剂分离的盐[Li（12-冠-4）2][PR'BMes 2]-THF（R'= Ph（13），Cy（14），Mes（15））。此外，Mes 2BF与[Li（THF）2 P（SiMe 3）2] 2的反应得到[Li（THF）3 P（SiMe 3）BMes 2]（16），其中Me 3SiF而不是LiF被消除。此外，TripBBr 2和2当量的LiPHMes之间的反应得到锂盐[Li（Et 2 O）2 P（Mes）B（PMesH）Trip]（17），涉及通过单键和多键结合到两个磷中心的硼。除了”B和31 P NMR光谱表征之外，还对二聚化合物1、锂盐[Li（Et 2 O）2 P（？）Bu）BTrip2]（9）、[Li（THF）3P（SiMe3）BMes2]（16）和[Li-（Et2O）2P（Mes）B（PHMes）Trip]（17）。化合物10-12和13-15，包括11、12和15的结构，已经在初步通信中描述。锂化合物7-17特别令人感兴趣，因为它们是已知的唯一结构特征为硼和磷之间涉及高度多重键合的化合物。因此，化合物17也是值得注意的，因为它具有迄今报道的最短BP键长，1.810（3）π。在130 K下具有Mo K η辐射（= 0.71069 A）的晶体数据：1，a= 10.291（4）A，B= 10.468（3）A，c= 14.767（2）A，a= 71.05（2），y = 75.63（2），y= 82.49（3），三斜晶系，空间群P1，Z= 0.00000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000
The synthesis and spectroscopic and structural characterization of several lithium salts of boryl phosphides and their precursors are described. Treatmentof the lithium salt of a primary phosphane H2PR'with R2BX (X= F, Cl) affords the phosphinoboranes (borylphosphanes) R2BPHR'(R/R'= Ph/r-Bu (1), Mes/r-Bu (2), Trip/r-Bu (3), Mes/Ph (4), Mes/Cy (5), Mes/Mes (6)(Mes= 2, 4, 6-Me3C6H2, Trip= 2, 4, 6-¡-Pr3C6H2, Cy= cyclohexyl)) in good yield. The reaction of compounds 1-6 with 1 equiv of n-BuLi or t-BuLi affords their corresponding lithium salts [Li (Et20) 2PR'BR2](7-12). The addition of 2 equiv of 12-crown-4 to Li (Et20) 2PR'BMes2 (R'= Ph (10), Cy (11), Mes (12)) gives the solvent-separated salts [Li (12-crown-4) 2][PR'BMes2]-THF (R'= Ph (13), Cy (14), Mes (15)). Also, the reaction of Mes2BF with [Li (THF) 2P (SiMe3) 2] 2 gives [Li (THF) 3P (SiMe3) BMes2](16) with elimination of Me3SiF rather than LiF. In addition, the reaction between TripBBr2 and 2 equiv of LiPHMes gave the lithium salt [Li (Et20) 2P (Mes) B (PMesH) Trip](17), involvingboron bound to two phosphorus centers through a single and a multiple bond. Apart from" B and 31P NMR spectroscopic characterization, the X-ray structures of the dimeric compound 1, the lithium salts [Li (Et20) 2P (?-Bu) BTrip2](9),[Li (THF) 3P (SiMe3) BMes2](16), and [Li-(Et20) 2P (Mes) B (PHMes) Trip](17) are described. Compounds 10-12 and 13-15, including the structures of 11, 12, and 15, have been described in a preliminary communication. The lithium compounds 7-17 are of particular interest because they are the only structurally characterizedcompounds known to involve a high degree ofmultiple bondingbetween boron and phosphorus. Thus, compound 17 is also notable since it has the shortest BP bond length, 1.810 (3) Á, reported to date. Crystal data with Mo K «radiation (= 0.71069 A) at 130 K: 1, a= 10.291 (4) A, b= 10.468 (3) A, c= 14.767 (2) A, a= 71.05 (2), ß= 75.63 (2), y= 82.49 (3), triclinic, space group P\, Z=