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Metal-Element Multiple Bonds Stabilized by Trisamidophosphines: Synthesis, Structure and Reactivity

三酰胺膦稳定的金属元素多重键：合成、结构和反应性

基本信息

批准号：
260640566
负责人：
Privatdozent Dr. Joachim Ballmann
金额：
--
依托单位：
Anorganisch-Chemisches Institut
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2014
资助国家：
德国
起止时间：
2013-12-31 至 2016-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/260640566?language=en
关键词：
Metal Element Multiple Bonds Stabilized

项目摘要

Numerous chemical transformations, such as alkene or alkyne metathesis, rely on metal complexes with multiply-bound heteroelements (E), which often play key roles in these trans-formations. The studies proposed herein are focused on group (IV) and group (V) metal complexes that contain M=ER and ME building blocks (E = CR, N, P, As, etc.) with metal-element double and triple bonds. In order to stabilize the reactive ME fragments, the use of trisamidophosphine ligand scaffolds is planned. As the latter ligands have been studied in detail already, the intended synthetic efforts are directed mainly towards the coordination chemistry of this new class of ligands and the reactivity of ME motifs. Anionic alkylidenes, imides and phosphinidenes of titanium, zirconium and hafnium are targeted initially and subsequent reactivity studies are meant to exploit the expected nucleophilicity of such M=ER anions (M = Ti, Zr, Hf; E = N, P, As) in order to reveal potential applications of these compounds. The synthesis of anionic vanadium, niobium and tantalum complexes with terminal nitrido, phosphido and arsenido moieties is going to play a crucial role as well. The development of new synthetic pathways to complexes containing ME triple bonds (M = V, Nb, Ta; E = N, P, As) is of fundamental relevance, while reactivity studies will gain in importance over the course of the work. In the long term, the latter reactivity studies are meant to discover and establish applications of such metal complexes, for example in homogeneous catalysis. As M=SiR2 and M=BR substructures have not been studied in much detail in case of early transition metals, the frontier-crossing use of trisamidophosphins to stabilize such structural motifs will be examined and directed towards possible applications of these systems.

许多化学转化，如烯烃或炔烃的复分解，依赖于具有多键杂元素（E）的金属配合物，它们通常在这些转化中起关键作用。本文提出的研究集中在含有M=ER和ME结构单元（E = CR、N、P、As等）的第（IV）族和第（V）族金属配合物。具有金属元素双键和三键。为了稳定反应性ME片段，计划使用三氨基膦配体支架。由于后者的配体已经详细研究，预期的合成努力主要是针对这类新的配体的配位化学和ME基序的反应性。最初针对钛、锆和铪的阴离子亚烷基、酰亚胺和膦酰亚胺，随后的反应性研究意在利用这些M=ER阴离子（M = Ti、Zr、Hf; E = N、P、As）的预期亲核性，以揭示这些化合物的潜在应用。同时，具有末端氮基、磷基和砷基的钒、铌和钽的阴离子配合物的合成也将起到至关重要的作用。开发新的合成途径，以配合物含有ME三键（M = V，Nb，Ta; E = N，P，As）是根本的相关性，而反应性的研究将获得的重要性在工作过程中。从长远来看，后者的反应性研究旨在发现和建立这种金属络合物的应用，例如在均相催化中。由于M= SiR 2和M=BR的子结构还没有在早期过渡金属的情况下进行了详细的研究，前沿交叉使用的trisamidophosphins稳定这样的结构图案将被检查，并针对这些系统的可能应用。