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Synthetic Entries to Early-Transition Metal Complexes Containing Terminal and Reactive Metal-Ligand Multiple Bonds

Synthetic Entries to Early-Transition Metal Complexes Containing Terminal and Reactive Metal-Ligand Multiple Bonds
含有末端和活性金属-配体多重键的早期过渡金属配合物的合成
批准号:
0848248
负责人:
Daniel Mindiola
金额:
$51.9万
依托单位:
依托单位国家:
美国
项目类别:
Continuing Grant
财政年份:
2009
资助国家:
美国
项目状态:
已结题
起止时间:
2009-02-01 至 2012-01-31

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中文摘要
翻译
无机和有机化学计划的这项研究奖支持印第安纳州大学的丹尼尔J. Mindiola教授的工作,以了解高度极化和反应性金属配体多重键的行为。 具有N(氮化物)、P(氮化物)、N(氮化物)、P(氮化物)和N(氮化物)的过渡金属配合物的瞬态和末端第4和5族过渡金属配合物的动力学和反应性研究(磷化物),CR2(亚烷基)和CR具有不饱和和饱和分子的(次烷基)部分有望揭示金属-配体多重键在化学惰性分子如烷烃,芳烃,N-杂环以及许多其他对活化和官能化具有极强抗性的小分子。 通过多电子氧化还原方法,通过结合已知的有机金属转化或通过配体框架的修饰,合成由早期3d金属组成的其他未知金属-配体多键支架的新合成策略的组合也将揭示前所未有的化学和新的转化。 通过制备具有金属-配体多重键的高价化合物,正在进行的研究有望开发新的系统,该系统可以掩盖低价金属中心以及催化反应,如甲烷活化和官能化,苯环开环和聚合,氢氟碳化合物的脱氢,以及N-杂环的官能化。 除了化学研究,布卢明顿的印第安纳州大学还成立了一个以学生为基础的分会,目的是招募代表性不足的群体进入物理科学。 在这些实验室接受培训的学生有望代表新一代化学家,他们可以制备设计用于携带特定功能的分子,同时节省能量。然而,分子是反应性的,产生较少的废物,并改进了工业环境中使用的当前实践。 以原子经济的方式进行合成和反应,代表了计划的标准目标之一,特别是在这个设计替代能源的不确定时代。 因此,在学生了解他们的系统如何运作后,他们能够使他们的试剂更有效地实现其设计的特定目标。
英文摘要
This Research award in the Inorganic and Organometallic Chemistry program supports work by Professor Daniel J. Mindiola at Indiana University to understand the behavior of highly polarized and thus reactive metal-ligand multiple bonds. Kinetics and reactivity studies of transient and terminal group 4 and 5 transition metal complexes having N (nitride), P (phosphide), CR2 (alkylidene) and CR (alkylidyne) moieties with unsaturated and saturated molecules are expected to reveal the role of the metal-ligand multiple bond during the activation of chemical inert molecules such as alkanes, arenes, N-heterocycles among many other small molecules that are exceedingly resistant towards activation and functionalization. The combination of new synthetic strategies to synthesize other unknown metal-ligand multiply bonded scaffolds composed of early 3d metals by a multielectron redox approach, by combining known organometallic transformations, or by modification of the ligand framework, will also unmask unprecedented chemistry and new transformations. By preparing high-valent compounds with metal-ligand multiple bonds the research being conducted is expected to develop new systems that can mask low-valent metal centers as well as catalyze reactions such as methane activation and functionalization, benzene ring-opening and polymerization, dehydrofluorination of hydrofluorocarbons, and the functionalization of N-heterocycles. In addition to chemical research a student based chapter developed at Indiana University, Bloomington, has been founded with the purpose of recruiting underrepresented groups into the physical sciences. Students trained in these laboratories are expected to represent a new generation of chemists who can prepare molecules designed to carry a specific function while conserving energy. However, the molecules are reactive, produce less waste and improve upon current practices used in the industrial setting. Synthesis and reactivity, in an atom-economical way, represents one of the program standard goals, especially now during this uncertain era for devising alternative sources of energy. Hence, after students understand how their system operates, they are able to make their reagent more efficient in achieving the specific goal for which it was designed.
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CAS: Synthetic Entries to ETM with M-Ligand Multiple Bonds and Their Role in Stoichiometric and Catalytic Carbon-Hydrogen Activation and Functionalization of Volatile Alkanes
  • 批准号:
    2154620
  • 项目类别:
    Standard Grant
  • 资助金额:
    $52.5万
  • 财政年份:
    2022
  • 负责人:
    Daniel Mindiola
  • 依托单位:
MRI: Acquisition of an X-ray Absorption Fine Structure (XAFS) source for Chemical and Spectroscopic Research and Training at the University of Pennsylvania
  • 批准号:
    2117783
  • 项目类别:
    Standard Grant
  • 资助金额:
    $28.39万
  • 财政年份:
    2021
  • 负责人:
    Daniel Mindiola
  • 依托单位:
Constructing Metal-Carbon Multiple Bonds for Dehydrogenation and Dehydrocoupling Reactions Involving Volatile Hydrocarbons
  • 批准号:
    1764329
  • 项目类别:
    Continuing Grant
  • 资助金额:
    $45.0万
  • 财政年份:
    2018
  • 负责人:
    Daniel Mindiola
  • 依托单位:
Metal-Ligand Multiple Bonds, Dehydrogenation Chemistry and Catalytic Transformations of Small Molecules Such as Methane, Ethane, Other Hydrocarbons, and N2
  • 批准号:
    1464659
  • 项目类别:
    Continuing Grant
  • 资助金额:
    $43.5万
  • 财政年份:
    2015
  • 负责人:
    Daniel Mindiola
  • 依托单位:
海外基金