Interactions of Verkade's Superbase with Strong Lewis Acids: From Labile Mono- and Binuclear Lewis Acid-Base Complexes to Phosphenium Cations

被引：33

作者：

Mummadi, Suresh ^{[1
]}

Kenefake, Dustin ^{[1
]}

Diaz, Rony ^{[1
]}

Unruh, Daniel K. ^{[1
]}

Krempner, Clemens ^{[1
]}

机构：

[1] Texas Tech Univ, Dept Chem & Biochem, Box 1061, Lubbock, TX 79409 USA

来源：

INORGANIC CHEMISTRY | 2017年 / 56卷 / 17期

基金：

美国国家科学基金会;

关键词：

RAY CRYSTAL-STRUCTURES; DIRECT ALPHA-ARYLATION; EFFICIENT PROMOTER; PHOSPHORUS-COMPOUNDS; CATALYZED AMINATION; ORGANIC SUPERBASE; ARYL; PROAZAPHOSPHATRANE; PAIRS; P(RNCH2CH2)(3)N;

D O I：

10.1021/acs.inorgchem.7b01719

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A series of mono- and binuclear Lewis acidbase complexes of the formulas N[CH2CH2N(Pr-i)](3)P -> LA [LA = BH3 (8), Ga(C6F5)(3) (10), GaCl3 (11)], LA -> N[CH2CH2N(Pr-i)](3)P [LA = Al(C6F5)(3) (6a), AlMe3 (6b), AlEt3 (6c), AlBu3i (6d), BF3 (13)], and LA <- N[CH2CH2N(Pri)](3)P -> LA [Lewis acid (LA) = Al(C6F5)(3) (7a), AlMe3 (7b), AlEt3 (7c), AlBu3i (7d), AlCl3 (7e), BH3 (9)] were generated from reactions of Verkades base, N[CH2CH2N(Pr-i)](3)P (1), with various boron-, aluminum-, and gallium-containing Lewis acids, and characterized by multinuclear NMR spectroscopy. {N[CH2CH2N(Pr-i)](3)P -> C7H7}[BF4] (5) was synthesized via the treatment of 1 with [C7H7][BF4]. The reaction of 1 with B(C6F5)(3), followed by the addition of [Ph3C](2)[B12Cl12], gave rise to the rearranged borate salt [PN4C9H17(Pr-i)(2)][B(12)Cl(1)2] (3), while treating 1 with [Ph3C]2[B12Cl12] exclusively afforded {N[CH2CH2N(Pr-i)](3)PH}(2)[B12Cl12] (4). Reactions of 1 with 2 equiv of GaCl3 and BF3, respectively, afforded the novel phosphenium gallate and borate salts 12a, 12b, and 15. The solid-state structures of 1, 35, 6b, 7a, 7b, 7e, 8, 10, 11, 12b, 13, and 15 were determined by X-ray crystallography.

引用

页码：10748 / 10759

页数：12

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