首页> 外文期刊>Coordination chemistry reviews >Ruthenium complexes of 1,4,7-trimethy1-1,4,7-triazacyclononane for atom and group transfer reactions
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Ruthenium complexes of 1,4,7-trimethy1-1,4,7-triazacyclononane for atom and group transfer reactions

机译:1,4,7-三甲基1-1,4,7-三氮杂环壬烷的钌配合物用于原子和基团转移反应

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摘要

With support by macrocyclic tertiary amine ligand l,4,7-trimethyl-l,4,7-triazacyclononane (Me3tacn), a number of mononuclear metal-ligand multiple bonded complexes have been isolated. Starting with a brief summary of these complexes, the present review focuses on ruthenium-oxo and -imido complexes of Me_3tacn. A family of monooxoruthenium(IV) complexes [Ru~(IV)(Me_3tacn)O(N-N)]~(2+) (N-N-2,2'-bipyridines) and a cis-dioxoruthenium(VI) complex ds-[Ru~(VI)(Me3tacn)O_2(CF_3CO_2)]~+ have been isolated, and the structures of [Ru~(lv)(Me_3tacn)0(bpy)](C10_4)2 (bpy=2,2'-bipyridine) and ris-[Ru~(vl)(Me_3tacn)02(CF_3C02)]C104 have been determined by X-ray crystallography. Oxidation of [Rul"(Me_3tacn)(NHTs)_2(OH)] (Ts-p-toluenesulfonyl) with Ag~+ and electrochemical oxidation of [Ru~(Ⅲ)(Me3tacn)(H2L)](C10_4)2 (H_3L-a-(l-amino-l-methylethyl)-2-pyridinemethanol) are likely to generate ruthenium-imido complexes supported by Me3tacn. DFT calculations on cis-[Ru~(Ⅵ)(Me3tacn)O_2(CF3CO_2)]~+ and proposed ruthenium-imido complexes have been performed. Complexes [Ru~(lv)(Me3tacn)O(N-N)]~(2+) are reactive toward alkene epoxidation, and cis-[Ru~(vl)(Me_3tacn)O_2(CF_3CO2)]~+ efficiently oxidizes various organic substrates including concerted [3+2] cycloaddition reactions with alkynes and alkenes to selectively afford α,β-diketones, cis-diols, or C=C bond cleavage products. Related oxidation reactions catalyzed by ruthenium Me_3tacn complexes include epoxidation of alkenes, cis-dihydroxylation of alkenes, oxidation of alkanes, alcohols, aldehydes, and arenes, and oxidative cleavage of C=C, C=C, and C-C bonds, all of which exhibit high selectivity. Ruthenium Me_3tacn complexes are also active catalysts for amination of saturated C-H bonds.
机译:在大环叔胺配体1,4,7-三甲基-1,4,7-三氮杂环壬烷(Me3tacn)的支持下,已分离出许多单核金属-配体多重键合复合物。从这些配合物的简要概述开始,本综述着重于Me_3tacn的钌-氧代和-亚氨基配合物。一族一氧杂钌(IV)配合物[Ru〜(IV)(Me_3tacn)O(NN)]〜(2+)(NN-2,2'-联吡啶)和一个顺式-二氧杂钌(VI)配合物ds- [Ru 〜(VI)(Me3tacn)O_2(CF_3CO_2)]〜+已分离,[Ru〜(lv)(Me_3tacn)0(bpy)](C10_4)2(bpy = 2,2'-联吡啶)的结构ris- [Ru〜(vl)(Me_3tacn)02(CF_3CO2)] C104已通过X射线晶体学测定。用Ag〜+氧化[Rul“(Me_3tacn)(NHTs)_2(OH)](Ts-对甲苯磺酰基)和[Ru〜(Ⅲ)(Me3tacn)(H2L)](C10_4)2(H_3L)的电化学氧化-a-(1-氨基-1-甲基乙基)-2-吡啶甲醇)可能生成Me3tacn支持的钌-亚氨基配合物。对顺式[[Ru〜(Ⅵ)(Me3tacn)O_2(CF3CO_2)]〜+的DFT计算[Ru〜(lv)(Me3tacn)O(NN)]〜(2+)对烯烃环氧化有反应性,而顺式[Ru〜(vl)(Me_3tacn)O_2( CF_3CO2)]〜+有效地氧化各种有机底物,包括与炔烃和烯烃的协同[3 + 2]环加成反应,以选择性地提供α,β-二酮,顺式二醇或C = C键裂解产物,钌催化相关的氧化反应。 Me_3tacn络合物包括烯烃的环氧化,烯烃的顺式二羟基化,烷烃,醇,醛和芳烃的氧化,以及C = C,C = C和CC键的氧化裂解,所有这些均表现出高选择性。配合物也是饱和C-H键胺化的活性催化剂。

著录项

  • 来源
    《Coordination chemistry reviews》 |2011年第8期|p.899-919|共21页
  • 作者单位

    Department of Chemistry and State Key Laboratory on Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong;

    Department of Chemistry and State Key Laboratory on Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong;

    Department of Chemistry and State Key Laboratory on Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong;

    Department of Chemistry and State Key Laboratory on Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong;

    Department of Chemistry and State Key Laboratory on Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong;

  • 收录信息 美国《科学引文索引》(SCI);美国《生物学医学文摘》(MEDLINE);
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

    Ruthenium; 1,4,7-Trimethyl-l ,4,7-triazacyclononane; (Me_3tacn); Ruthenium-oxo and -imido complexes;

    机译:钌;1,4,7-三甲基-1,4,7-三氮杂环壬烷;(Me_3tacn);钌-氧代和-亚氨基配合物;
  • 入库时间 2022-08-18 03:00:56

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