Bonding and Reactivity in Terminal versus Bridging Arenide Complexes of Thorium Acting as ThII Synthons

被引：20

作者：

Hsueh, Fang-Che ^{[1
]}

Rajeshkumar, Thayalan ^{[2
]}

Kooij, Bastiaan ^{[3
]}

Scopelliti, Rosario ^{[1
]}

Severin, Kay ^{[3
]}

Maron, Laurent ^{[2
]}

Zivkovic, Ivica ^{[4
]}

Mazzanti, Marinella ^{[1
]}

机构：

[1] Ecole Polytech Fed Lausanne EPFL, Inst Sci & Ingn Chim, Grp Coordinat Chem, CH-1015 Lausanne, Switzerland

[2] Inst Natl Sci Appl, Lab Phys & Chim Nanoobjets, F-31077 Toulouse 4, France

[3] Ecole Polytech Fed Lausanne EPFL, Inst Sci & Ingn Chim, Lab Supramol Chem, CH-1015 Lausanne, Switzerland

[4] Ecole Polytech Fed Lausanne EPFL, Inst Phys, Lab Quantum Magnetism, CH-1015 Lausanne, Switzerland

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2023年 / 62卷 / 09期

基金：

瑞士国家科学基金会;

关键词：

Actinides; Inverse-Sandwich Complexes; Redox Reactivity; Redox-Active Ligands; Thorium; MULTIPLE BONDS; METAL; REDUCTION; OXO; METALLOCENE; OXIDATION; CLEAVAGE; LIGANDS; ARENES; STATE;

D O I：

10.1002/anie.202215846

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Thorium redox chemistry is extremely scarce due to the high stability of Th-IV. Here we report two unique examples of thorium arenide complexes prepared by reduction of a Th-IV-siloxide complex in presence of naphthalene, the mononuclear arenide complex [K(OSi((OBu)-Bu-t)(3))(3)Th(eta(6)-C10H8)] (1) and the inverse-sandwich complex [K(OSi((OBu)-Bu-t)(3))(3)Th](2)(mu-eta(6),eta(6)-C10H8)] (2). The electrons stored in these complexes allow the reduction of a broad range of substrates (N2O, AdN(3), CO2, HBBN). Higher reactivity was found for the complex 1 which reacts with the diazoolefin IDipp=CN2 to yield the unexpected Th-IV amidoalkynyl complex 5 via a terminal N-heterocyclic vinylidene intermediate. This work showed that arenides can act as convenient redox-active ligands for implementing thorium-ligand cooperative multielectron transfer and that the reactivity can be tuned by the arenide binding mode.

引用

页数：11

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