Zirconium-Nitrogen Intermolecular Frustrated Lewis Pairs

被引：17

作者：

Hamilton, Hugh B. ^{[1
]}

King, Ashley M. ^{[1
]}

Sparkes, Hazel A. ^{[1
]}

Pridmore, Natalie E. ^{[1
]}

Wass, Duncan F. ^{[2
]}

机构：

[1] Univ Bristol, Sch Chem, Cantocks Close, Bristol BS8 1TS, Avon, England

[2] Cardiff Univ, Sch Chem, Cardiff Catalysis Inst, Main Bldg,Pk Pl, Cardiff CF10 3AT, S Glam, Wales

来源：

INORGANIC CHEMISTRY | 2019年 / 58卷 / 09期

基金：

英国工程与自然科学研究理事会;

关键词：

HYDROGEN ACTIVATION; CHEMISTRY; REACTIVITY; POLYMERIZATION; BEHAVIOR; BASE; ACID; CO2;

D O I：

10.1021/acs.inorgchem.9b00569

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A series of intermolecular transition metal frustrated Lewis pairs (FLPs) based on zirconocene alkoxide complexes ([Cp2Zr(OMes)](+) 1 or ([Cp*Zr-2(OMes)](+)2) with nitrogen Lewis bases (NEt3, (NEtPr2)-Pr-i, pyridine, 2-methylpyridine, 2,6-lutidine) are reported. The interaction between Zr and N depends on the specific derivatives used, in general more sterically encumbered pairs leading to a more frustrated interaction; however, DOSY NMR spectroscopy reveals these interactions to be dynamic in nature. The pairs with various amine bases undergo typical FLP-type reactivity with D-2, CO2, THF, and PhCCD. The catalytic dehydrocoupling of Me2NH center dot BH3 is also reported. Comparisons can be made with previous work employing phosphines as Lewis bases suggesting that hard-hard or hard-soft acid-base considerations are of little importance compared to the more prominent roles of steric bulk and basicity.

引用

页码：6399 / 6409

页数：11

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