稳定单重态卡宾作为过渡金属中心的模拟物。
Stable singlet carbenes as mimics for transition metal centers.
作者信息
Martin David, Soleilhavoup Michele, Bertrand Guy
机构信息
UCR-CNRS Joint Research Chemistry Laboratory (UMI 2957), Department of Chemistry, University of California, Riverside, California, 92521-0403, USA; Tel: +1 951 827 2719.
出版信息
Chem Sci. 2011 Jan 1;2(3):389-399. doi: 10.1039/C0SC00388C.
Abstract
This perspective summarizes recent results, which demonstrate that stable carbenes can activate small molecules (CO, H(2), NH(3) and P(4)) and stabilize highly reactive intermediates (main group elements in the zero oxidation state and paramagnetic species). These two tasks were previously exclusive for transition metal complexes.
摘要
本文综述了近期的研究成果，这些成果表明稳定的卡宾能够活化小分子（CO、H₂、NH₃和P₄）并稳定高活性中间体（零氧化态的主族元素和顺磁性物种）。这两项任务以前是过渡金属配合物所独有的。
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本文引用的文献
1
Trisilaallene and the Relative Stability of Si3H4 Isomers.三硅烯和 Si3H4 异构体的相对稳定性。
J Chem Theory Comput. 2006 Jul;2(4):956-64. doi: 10.1021/ct050154a.
2
The reaction of dimethylsilylene with carbon monoxide in low-temperature matrices.低温基质中二甲基硅烯与一氧化碳的反应。
J Am Chem Soc. 1988 Aug 1;110(18):6240-1. doi: 10.1021/ja00226a046.
3
Coordination chemistry at carbon.碳的配位化学。
Nat Chem. 2009 Jul;1(4):295-301. doi: 10.1038/nchem.248. Epub 2009 Jun 14.
4
Chemical bonding: Rethinking carbon.化学键合：对碳的重新思考。
Nat Chem. 2009 Jul;1(4):265-6. doi: 10.1038/nchem.265.
5
Pi-bonding and the lone pair effect in multiple bonds involving heavier main group elements: developments in the new millennium.涉及较重主族元素的多重键中的π键合与孤对效应：新千年的进展
Chem Rev. 2010 Jul 14;110(7):3877-923. doi: 10.1021/cr100133q.
6
A crystalline phosphinyl radical cation.一个磷酰自由基阳离子。
J Am Chem Soc. 2010 Aug 4;132(30):10262-3. doi: 10.1021/ja1046846.
7
A different view of coordination chemistry: bis(carbene) adducts of (P[triple bond]N) and (P[triple bond]N)+.配位化学的一种不同观点：(P≡N) 和 (P≡N)+ 的双（卡宾）加合物
Angew Chem Int Ed Engl. 2010 Aug 9;49(34):5829-30. doi: 10.1002/anie.201003479.
8
Isolation of a carbene-stabilized phosphorus mononitride and its radical cation (PN+*).一种卡宾稳定的单磷氮化物及其自由基阳离子（PN+*）的分离
Angew Chem Int Ed Engl. 2010 Aug 9;49(34):5930-3. doi: 10.1002/anie.201002889.
9
Radical deoxygenation of xanthates and related functional groups with new minimalist N-heterocyclic carbene boranes.新型极简 N-杂环卡宾硼烷对黄原酸盐和相关官能团的彻底脱氧。
Org Lett. 2010 Jul 2;12(13):3002-5. doi: 10.1021/ol101015m.
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Org Lett. 2010 Jul 2;12(13):2998-3001. doi: 10.1021/ol101014q.
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