Zinc-Mediated Transmetalation as a Route to Anionic N-Heterocyclic Olefin Complexes in the p-Block

被引：13

作者：

Watson, Ian C. ^{[1
]}

Ferguson, Michael J. ^{[1
]}

Rivard, Eric ^{[1
]}

机构：

[1] Univ Alberta, Dept Chem, Edmonton, AB T6G 2G2, Canada

来源：

INORGANIC CHEMISTRY | 2021年 / 60卷 / 23期

基金：

加拿大自然科学与工程研究理事会; 加拿大创新基金会;

关键词：

ZETA VALENCE QUALITY; GAUSSIAN-BASIS SETS; METALLACYCLE TRANSFER; CRYSTAL-STRUCTURE; ATOMS LI; REACTIVITY; PHOSPHINE; CHEMISTRY; PATHWAY; CATIONS;

D O I：

10.1021/acs.inorgchem.1c02961

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Anionic N-heterocyclic olefins (aNHOs) are suited well for the stabilization of low-coordinate inorganic complexes, due to their steric tunability and strong sigma- and pi-electron donating abilities. In this study, the new two-coordinate zinc complex ((Me)eIPFCH)(2)Zn ((IPrCH)-I-Me = [(MeCNDipp)(2)C=CH](-), Dipp = 2,6-diisopropylphenyl) is shown to participate in a broad range of metathesis reactions with main group element-based halides and hydrides. In the case of the group 14 halides, Cl2E.dioxane (E = Ge and Sn), transmetalation occurs to form dinuclear propellane-shaped cations, [((IPICHE)-I-Me)(2)(mu-Cl](+), while the aNHO-capped phosphine ligand (IPrCH)-I-Me-PPh2 is obtained when ((Me)lPrCH)(2)Zn is combined with CIPPh2. Lastly, ZnH2 elimination drives transmetalation between ((Me)lPrCH)(2) Zn and hydroboranes and hydroalumanes, leading to Lewis acidic aNHO-supported -boryl and -alane products.

引用

页码：18347 / 18359

页数：13

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