AN NMR-STUDY OF THE REACTIONS OF PHOSPHORUS(III) HALIDES WITH HALIDE ION ACCEPTORS - 2-COORDINATE PHOSPHORUS CATIONS WITH BULKY LIGANDS
AN NMR-STUDY OF THE REACTIONS OF PHOSPHORUS(III) HALIDES WITH HALIDE ION ACCEPTORS - 2-COORDINATE PHOSPHORUS CATIONS WITH BULKY LIGANDS
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DOI：
10.1021/ic50223a034
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发表时间：
1981-01-01
影响因子：
4.6
通讯作者：
WILBURN, JC
中科院分区：
文献类型：
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作者：
COWLEY, AH;LATTMAN, M;WILBURN, JC
用化学计量比的A12C16在CH2C12溶液中处理前驱体氯化物制备了Bu)2P]+。阳离子[(Me2N)(z-Bu)P]+在两个方面值得注意。首先，它具有PC键，其次，31p的化学位移(+513.2 ppm)是迄今报道的最大的化学位移值。在变温核磁共振数据的基础上讨论了新阳离子的立体化学。(z-Bu)(Me_3Si)_2NPCl与A12C16反应或(z-Bu)(Me_3Si)_2NPF与PF5反应制备阳离子[(Z-Bu)(Me_3Si)_2NP]+是不可能的。这两个反应都生成了P键合的Lewis酸碱络合物。(t-Bu)Me2NPF与PFS的反应对反应物的化学计量很敏感，生成了不同量的酸碱配合物(z-Bu)(Me2N)(F)P-*-PF5和[(z-Bu)(Me2N)(F)P-P(z-Bu)(NMe2)]+。
Bu) 2P]+ have been prepared by treatment of the respective precursor chlorides with the stoichiometricquantity of A12C16 in CH2C12 solution. The cation [(Me2N)(z-Bu) P]+ is noteworthy in two respects. First, it features a PC bond, and, second, the 31P chemical shift (+ 513.2 ppm) is the largest such value ever reported. The stereochemistries of the new cations are discussed on the basis of variable-temperature NMR data. It was not possible to prepare the cation [(Z-Bu)(Me3Si) 2NP]+ by treatment of (z-Bu)(Me3Si) 2NPCl with A12C16, or by the reaction of (z-Bu)(Me3Si) 2NPF with PF5. Both reactions resulted in P-bonded Lewis acid-base complexes. The reaction of (t-Bu) Me2NPF with PFS is sensitive to reactant stoichiometry and yields varying amounts of the acid-base complexes (z-Bu)(Me2N)(F) P-*-PF5 and [(z-Bu)(Me2N)(F) P—P (z-Bu)(NMe2)]+.