Gold(I) Complexes Containing Unsaturated Hydrocarbyl Ligands

含有不饱和烃基配体的金(I)配合物

基本信息

批准号：
2102653
负责人：
Ross Widenhoefer
金额：
$ 45万
依托单位：
Duke University
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2021
资助国家：
美国
起止时间：
2021-09-01 至 2024-08-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102653&HistoricalAwards=false
关键词：
Gold Complexes Containing Unsaturated Hydrocarbyl

项目摘要

In this project funded by the Chemical Structure, Dynamics and Mechanisms B Program of the Chemistry Division, Professor Ross A. Widenhoefer in the Department of Chemistry at Duke University will investigate new chemistry of neutral gold(I) complexes. The project focuses on unsaturated hydrocarbyl ligands including sigma-alkenyl, -allyl, -allenyl, and -propargyl ligands. One goal of this research is to develop a meaningful understanding of the structures and fluxional behavior of these complexes and, likewise an understanding of the mechanisms through which these complexes undergo electrophilic deauration (loss of gold). In doing so, these activities will provide mechanistic insight that will serve the ever growing global community of researchers working toward (1) the development of new and more efficient gold(I) catalyzed transformations and (2) elucidation of the mechanisms of gold(I)-catalyzed transformations. The proposed research activities are fully integrated into the scientific education and training of the graduate and undergraduate student researchers, including students from ethnic groups traditionally underrepresented in the sciences. Graduate students are encouraged to augment their graduate research and educational experience through participation in educational activities offered through the Duke University Graduate School. Graduate students will participate in community outreach activities in collaboration with Dr. Ben Bobay of the Duke NMR center, directed toward providing local high school students with hands-on exposure to modern high-field NMR spectroscopy and one-on-one instruction in the processing, manipulation, and interpretation of NMR data.Despite a growing body of research in this area, limited experimental information is available regarding the structure, reactivity, and fluxional behavior of gold complexes containing unsaturated hydrocarbyl ligands including sigma-alkenyl, -allyl, -allenyl, and -propargyl ligands. The proposed research activities aim to fill these gaps and develop an experimentally-grounded understanding of gold complexes containing unsaturated hydrocarbyl ligands. Focus is on understanding the structure and fluxional behavior of these complexes and the mechanisms of electrophilic deauration. The research will address two areas of inquiry. The first area involves the elucidation of the mechanisms for the addition of electrophiles to gold alkenyl complexes involving direct attack on the C=C alkenyl bond by (i) validating the pi-alpha pathway for electrophilic addition, (ii) validating the pi-beta pathway for electrophilic addition, and (iii) modeling the transition state/intermediate for alkyne/alkene cycloaddition. The second area involves the elucidation of the structures, fluxional behavior and nucleophilic behavior of gold hydrocarbyl complexes possessing beta, gamma and or gamma, delta unsaturation, specifically targeting (i) gold sigma-allyl complexes, (ii) gold sigma-allenyl and sigma-propargyl complexes, and (iii) gold 3-butenyl complexes.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在这个由化学部化学结构、动力学和机理 B 项目资助的项目中，杜克大学化学系的 Ross A. Widenhoefer 教授将研究中性金（I）配合物的新化学。该项目重点关注不饱和烃基配体，包括σ-烯基、-烯丙基、-丙烯基和-炔丙基配体。这项研究的一个目标是对这些配合物的结构和流动行为产生有意义的理解，同样了解这些配合物经历亲电脱气（金损失）的机制。在此过程中，这些活动将提供机制见解，为不断增长的全球研究人员群体提供服务，这些研究人员致力于 (1) 开发新的、更高效的金 (I) 催化转化，以及 (2) 阐明金 (I) 的机制。 )-催化转化。拟议的研究活动完全融入研究生和本科生研究人员的科学教育和培训，包括来自传统上在科学领域代表性不足的族裔群体的学生。鼓励研究生通过参与杜克大学研究生院提供的教育活动来增加他们的研究生研究和教育经验。研究生将与杜克核磁共振中心的 Ben Bobay 博士合作参加社区外展活动，旨在为当地高中生提供现代高场核磁共振波谱的实践接触和处理过程中的一对一指导核磁共振数据的操作和解释。尽管该领域的研究不断增多，但有关含有不饱和烃基配体（包括σ-烯基）的金络合物的结构、反应性和流动行为的实验信息有限， -烯丙基、-丙烯基和-炔丙基配体。拟议的研究活动旨在填补这些空白，并对含有不饱和烃基配体的金配合物形成基于实验的理解。重点是了解这些配合物的结构和流动行为以及亲电脱气的机制。该研究将涉及两个调查领域。第一个领域涉及通过 (i) 验证亲电加成的 pi-alpha 途径，(ii) 验证 pi-beta 直接攻击 C=C 烯基键，阐明亲电试剂向金烯基配合物加成的机制亲电加成途径，以及（iii）模拟炔烃/烯烃环加成的过渡态/中间体。第二个领域涉及具有β、γ和/或γ、δ不饱和度的金烃基配合物的结构、流动行为和亲核行为的阐明，特别针对(i)金σ-烯丙基配合物，(ii)金σ-烯基和σ - 炔丙基配合物，以及 (iii) 金 3-丁烯基配合物。该奖项反映了 NSF 的法定使命，并被认为值得通过以下方式获得支持使用基金会的智力价值和更广泛的影响审查标准进行评估。