• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Coordination chemistry reviews >eta(3)-Allyl carbonyl complexes of group 6 metals: Structural aspects, isomerism, dynamic behaviour and reactivity
【24h】

eta(3)-Allyl carbonyl complexes of group 6 metals: Structural aspects, isomerism, dynamic behaviour and reactivity

机译：6族金属的eta（3）-烯丙基羰基配合物：结构方面，异构性，动力学行为和反应性

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

Transition metal complexes with pi-allylic ligands remain an attractive topic in organometallic chemistry, given the numerous reports of a wide variety of synthetic routes, dynamic behaviour and reactivity, structural (including isomerism), spectroscopic and redox properties, and applications in organic synthesis and catalysis. Surprisingly, despite the considerable interest in the rich and varied chemistry of this family of organometallic compounds, there is no recent review. This review is focused on pi-allylic representatives of low-cost Group-6 metals bearing one or more carbonyl ligand, the coordination sphere being complemented with eta(5)-cyclopentadienyl (Section 2), chelating ligands, including redox-active alpha-diimines and various complementary diphosphines (Section 3), and novel anionic amidinate or pyrazolate ligands (Section 4). In Section 1, particular attention is paid to rearrangements of the pi-allylic ligand, namely exo and endo isomerism, interconversion mechanisms, fluxionality, and agostic interactions. In addition, the application of multinuclear NMR spectroscopy to the elucidation of such isomerism, and the effect of the metal-centre oxidation state on the bonding, dynamic behaviour and reactivity of the pi-allylic ligand are described. The detailed mechanistic description of the synthetic routes and dynamic behaviour of selected representatives of alpha-diimine complexes in Section 2 is followed by a description of the [M(CO)(2)(eta(3)-allyl-H,R)(alpha-diimine)](0/+) fragment as a convenient scaffold for diverse monodentate ligands participating in a range of substitution, insertion, intramolecular migration and C-C coupling reactions - frequently involving also the pi-allylic ligand, such as allylic alkylation. Special attention is devoted to selected examples of redox and acid-base reactivity of the alpha-diimine complexes with emphasis on prospects in electrocatalysis. The amidinate (and related pyrazolate) ligands treated in Section 4 may directly replace the pi-allylic ligand in some cyclopentadienyl complexes (Section 2) or the alpha-diimine ligand in some dicarbonyl pi-allylic complexes (Section 3). The brief description of their synthetic routes is complemented by intriguing examples of fluxionality and characteristic reactivity encountered for these unusual four-electron donor ligands. Crown Copyright (C) 2016 Published by Elsevier B.V. All rights reserved.
机译：鉴于具有大量合成路线，动力学行为和反应性，结构（包括异构体），光谱和氧化还原特性以及在有机合成和化学中的应用的众多报道，具有π-烯丙基配体的过渡金属络合物在有机金属化学中仍然是一个有吸引力的话题。催化。令人惊讶地，尽管对该有机金属化合物家族的丰富和多样的化学有相当大的兴趣，但是最近没有评论。这项审查的重点是带有一个或多个羰基配体的低成本第6组金属的烯丙基代表，配位体由eta（5）-环戊二烯基（第2部分），螯合配体（包括氧化还原活性α-二亚胺和各种互补的二膦（第3节），以及新型的阴离子a基或吡唑酸酯配体（第4节）。在第1节中，特别注意了π-烯丙基配体的重排，即外向异构和内向异构，相互转化机制，流动性和不良相互作用。另外，描述了多核NMR光谱在阐明这种异构体中的应用，以及金属中心氧化态对π-烯丙基配体的键合，动力学行为和反应性的影响。在第2节中详细描述了合成的途径和选定的α-二亚胺配合物代表的动态行为，并附有[M（CO）（2）（eta（3）-allyl-H，R）（ α-二亚胺）]（0 / +）片段，是参与取代，插入，分子内迁移和CC偶联反应的各种单齿配体的简便支架-通常还涉及π-烯丙基配体，例如烯丙基烷基化。特别注意α-二亚胺配合物的氧化还原和酸碱反应性的选定实例，重点是电催化的前景。在第4节中处理过的in酰胺（和相关的吡唑酸酯）配体可以直接取代某些环戊二烯基配合物（第2节）中的π-烯丙基配体或某些二羰基π-烯丙基络合物中的α-二亚胺配体（第3节）。这些奇特的合成路线的简短描述得到了这些不寻常的四电子供体配体所遇到的流动性和特征反应性实例的补充。官方版权（C）2016，由Elsevier B.V.保留所有权利。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号