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
收藏
页码：18347 / 18359
页数：13
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