Cationic tetrylenes as Single-Center Ambiphile ligands for Cooperative N-H bond activation and hydroamination catalysis
阳离子四萘嵌苯作为单中心双亲配体用于协同 N-H 键活化和加氢胺化催化
基本信息
- 批准号:470323245
- 负责人:
- 金额:--
- 依托单位:
- 依托单位国家:德国
- 项目类别:Research Grants
- 财政年份:
- 资助国家:德国
- 起止时间:
- 项目状态:未结题
- 来源:
- 关键词:
项目摘要
Amines, which are indispensable building blocks in chemical synthesis, are produced on industrial scale through multi-step stoichiometric processes, thus generating considerable waste and using excessive energy. A process which overcomes this is the 100% atom efficient addition of ammonia to alkenes and alkynes. Homogenous catalytic systems for the selective synthesis of primary amines through hydroamination are essentially unknown, historically due to major challenges in the activation of N-H bonds at a transition metal (TM) center. The selective synthesis of secondary amines from primary amines and unactivated alkenes are also extremely rare on similar grounds. These two aspects of hydroamination therefore still stand as major challenges in catalysis to this day. This project aims to tackle these challenging processes through the development of a novel concept in ligand design and bond activation, namely cationic Single-Center Ambiphile ligands. These ligands can simultaneously act as σ-donors and strong π-acceptors, remaining Lewis-acidic when in the coordination sphere of a TM. This leads to a unique metal-ligand cooperative mechanism in N-H bond activation, where substrate binding occurs at the ligand as opposed to the metal, and so proceeding through an ‘Umpoled’ bond activation. The unique activation mechanism would lead to a TM-hydride complex through N-H bond scission, which can subsequently react with unsaturated substrates. We will develop and define this unique bond activation process, and take steps towards utilizing it in the catalytic hydroamination of alkenes with ammonia, to form primary amines, and in the subsequent selective generation of secondary amines. To achieve this, the present project will develop a novel class of cationic tetrylenes, which have the capacity to act as Single-Center Ambiphile ligands, specifically focusing on GeII and SnII, in conjunction with low-cost, highly abundant late first-row transition metals, Fe, Co, and Ni. Through differing metal-ligand combinations, as well as steric and electronic modifications of the ligands, we will develop a broad, well-defined set of systems for controlled N-H bond activation in ammonia and higher amines, and extend this to well-defined catalytic processes. To further define bond-activation mechanisms via which Single-Center Ambiphile ligand-TM systems can operate, we will also study the ‘Umpoled’ scission of further protic and hydridic E-H substrates (E = O, P, B, Si, H, etc.), as well as reactivity towards key catalytic substrates such as CO and CO2, in order to understand the effects of bond polarity in bond-activation by Single-Center Ambiphile systems. As a whole, this project aims to lay the foundations for the novel Single-Centre Ambiphile ligand concept, to ultimately develop systems which counter the poor atom economy of common industrial processes for amine synthesis.
胺是化学合成中不可或缺的基本组成部分,在工业规模上通过多步化学计量工艺生产,因此产生大量废物并使用过多的能源。克服这一点的方法是将氨100%原子有效地加成到烯烃和炔上。用于通过加氢胺化选择性合成伯胺的均相催化体系基本上是未知的,历史上是由于在过渡金属(TM)中心处的N-H键的活化中的主要挑战。基于类似的理由,从伯胺和未活化的烯烃选择性合成仲胺也是极其罕见的。因此,加氢胺化的这两个方面至今仍然是催化中的主要挑战。该项目旨在通过开发配体设计和键活化的新概念,即阳离子单中心双亲配体,来解决这些具有挑战性的过程。这些配体可以同时充当σ-供体和强π-受体,当在TM的配位球中时保持路易斯酸性。这导致N-H键活化中独特的金属-配体协作机制,其中底物结合发生在配体而不是金属处,并且因此通过“Umpoled”键活化进行。其独特的活化机制是通过N-H键断裂形成TM-氢化物络合物,随后与不饱和底物反应。我们将开发和定义这种独特的键活化过程,并采取措施利用它在催化加氢胺化烯烃与氨,形成伯胺,并在随后的选择性生成仲胺。为了实现这一目标,本项目将开发一种新型的阳离子tetrylenes,它有能力作为单中心双亲配体,特别是专注于GeII和SnII,结合低成本,高度丰富的后期第一行过渡金属,Fe,Co和Ni。通过不同的金属-配体组合,以及配体的空间和电子修饰,我们将开发一套广泛的,定义明确的系统,用于氨和高级胺中的受控N-H键活化,并将其扩展到定义明确的催化过程。为了进一步定义单中心双亲配体-TM系统可以操作的键活化机制,我们还将研究进一步的质子和双亲E-H底物(E = O,P,B,Si,H等)的“Umpoled”断裂,以及对关键催化底物如CO和CO2的反应性,以了解单中心双亲体系中键极性对键活化的影响。总的来说,该项目旨在为新的单中心双亲配体概念奠定基础,最终开发出对抗胺合成常见工业过程的原子经济性差的系统。
项目成果
期刊论文数量(0)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
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Dr. Terrance Hadlington, Ph.D.其他文献
Dr. Terrance Hadlington, Ph.D.的其他文献
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{{ truncateString('Dr. Terrance Hadlington, Ph.D.', 18)}}的其他基金
Sustainable Alkaline Earth-derived systems for multi-component coupling chemistry, and the exploration of fundamental molecular beryllium systems
用于多组分耦合化学的可持续碱土衍生系统以及基本分子铍系统的探索
- 批准号:
523956566 - 财政年份:
- 资助金额:
-- - 项目类别:
Research Grants
相似海外基金
Amphiphilic Tetrylenes in (asymmetric) Catalysis (A06)
(不对称)催化中的两亲性四萘嵌苯 (A06)
- 批准号:
159651657 - 财政年份:2010
- 资助金额:
-- - 项目类别:
Collaborative Research Centres