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.

在该项目由化学结构，动力学和机制B计划资助的项目中，杜克大学化学系的罗斯·Widenhoefer教授将研究中性黄金（I）综合体的新化学。该项目的重点是不饱和氢核酸配体，包括Sigma -Alkenyl，-AlyL，-allenyl和 - 丙酰藻配体。这项研究的目标之一是对这些复合物的结构和滤通行为有意义地理解，同样是对这些复合物经历亲电脱硫的机制的理解（黄金损失）。在这样做的过程中，这些活动将提供机械洞察力，为（1）开发新的，更有效的黄金（i）催化转化的新的研究人员社区，以及（2）阐明黄金（I）催化转化的机制。拟议的研究活动完全融入了研究生和本科生研究人员的科学教育和培训中，包括传统上在科学中人数不足的族裔学生。鼓励研究生通过参加通过杜克大学研究生院提供的教育活动来增强其研究生研究和教育经验。研究生将与Duke NMR中心的Ben Bobay博士合作参加社区宣传活动，致力于向当地的高中生提供动手接触现代的高档NMR NMR光谱和一对一的指导，并在处理，操作，操纵和对NMR的解释中的处理，操纵和解释NMR的培训中，该领域的越来越多。不饱和的氢碳纤维配体，包括Sigma -Alkenyl，-Alyl，-allenyyl和 - 丙型甲基配体。提出的研究活动旨在填补这些空白，并对含有不饱和氢碳二碳酸氢配体的黄金配合物的实验基础。重点是理解这些复合物的结构和流量行为以及电涂层的机制。该研究将解决两个询问领域。第一个区域涉及通过（i）通过（i）验证验证Pi-Alpha添加的Pi-Alpha途径，（ii）验证PI-BETA途径的电动添加和（III III）对过渡症进行过渡的pi-beta途径，涉及将电力添加到涉及C = C烷基键的金烷基络合物中的机制。第二个区域涉及具有β氢碳纤维复合物具有β，伽玛和 /或伽玛的结构，流量行为和亲核行为NSF的法定使命，并使用基金会的知识分子优点和更广泛的影响审查标准来评估值得支持。