Probing the Association of Frustrated Phosphine-Borane Lewis Pairs in Solution by NMR Spectroscopy

被引：83

作者：

Rocchigiani, Luca ^{[1
]}

Ciancaleoni, Gianluca ^{[2
]}

Zuccaccia, Cristiano ^{[1
]}

Macchioni, Alceo ^{[1
]}

机构：

[1] Univ Perugia, Dipartimento Chim Biol & Biotecnol, I-06123 Perugia, Italy

[2] Univ Perugia, Dipartimento Chim Biol & Biotecnol, Ist CNR Sci & Tecnol Mol, I-06123 Perugia, Italy

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 01期

关键词：

HYDROGEN ACTIVATION; CATALYTIC-HYDROGENATION; ION-PAIRS; COMPLEXES; REACTIVITY; DIHYDROGEN; DIFFUSION; MECHANISM; TENDENCY; BOND;

D O I：

10.1021/ja4119169

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

F-19,H-1 HOESY, diffusion, and temperature-dependent F-19 and H-1 NMR studies allowed us to unequivocally probe the association between the frustrated PR3/B(C6F5)(3) (1, R = CMe3; 2, R = 2,4,6-Me3C6H2) Lewis pairs in aromatic solvents. No preferential orientation is favored, as deduced by combining F-19,H-1 HOESY and DFT results, suggesting association via weak dispersion rather than residual acid/base interactions. The association process is slightly endoergonic [K = 0.5 M-1, Delta G(0) (298 K) = +0.4 kcal/mol for 2], as derived from diffusion NMR measurements.

引用

页码：112 / 115

页数：4

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