Gold complexes containing redox-active ambiphilic P/Sb ligands: Synthesis, structure and catalytic properties

含有氧化还原活性双亲 P/Sb 配体的金配合物：合成、结构和催化性能

• 批准号: 1566474
• 负责人: Francois Gabbai
• 金额: $ 48.26万
• 依托单位: Texas A&M University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-06-01 至 2019-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1566474&HistoricalAwards=false
• 关键词: Gold; complexes; containing; redox; active

With the support of the Chemical Synthesis Program of the Chemistry Division, Professor François Gabbaï of the Chemistry Department at Texas A&M University iinvestigates the chemistry of phosphine gold complexes that incorporate a Lewis acidic antimony atom as part of the ligand architecture. The goal of this project is to determine if the redox state of the antimony center can be used to modulate the Lewis acidity and catalytic properties of the gold center. This idea is being tested by investigating the catalytic properties of the complexes in the electrophilic activation of alkynes. Altogether, this research program helps to validate the notion that ligands combining a phosphine with an antimony center can be used for the construction of novel redox-responsive catalysts. In addition to contributing to the education of a diverse group of students, this project allows the principle investigator to maintain his involvement in various service and outreach activities involving K-6 students.A series of gold complexes featuring ambiphilic ligands containing phosphines as σ-donors and an antimony atom as a σ-acceptor are investigated with the ultimate goal of understanding whether the redox state of the antimony atom can be used to modulate the Lewis acidity and catalytic properties of the gold center. This idea is being tested by studying gold complexes featuring mono(phosphino)antimony and bis(phosphino)antimony ligands. For both type of complexes, oxidation of the antimony atom from the +III to the +V state is expected to activate the gold center and enhance its affinity for Lewis basic substrates including alkynes. The mono(phosphino)antimony derivatives is designed such that activation occurs by abstraction of a gold-bound halide ligand by the neighboring Lewis acidic antimony center. Activation of the complexes featuring a bis(phosphino)antimony ligand is expected to occur through formation of a direct Au→Sb interaction. For both families of complexes, the extent of activation experienced by the gold center is derived from an experimental determination of its Lewis acidity, as well as from its ability to catalyze reactions involving alkynes. At the heart of this project lies the fundamental notion that the redox state of antimony ligands can be manipulated as a means to adjust the reactivity of a transition metal center held in proximity by ancillary ligands. These fundamental advances may prove transformative in the area of redox-responsive ligands, with applications in sensing and catalysis. Another important outcome of this project is the involvement and education of a diverse group of students. The educational plan also includes outreach to students enrolled in Spanish/English K-6 dual language classes at local elementary and intermediate schools.

在化学系化学合成项目的支持下，德克萨斯农工大学化学系的 François Gabbaï 教授研究了含有路易斯酸性锑原子作为配体结构一部分的膦金配合物的化学性质。目的是确定锑中心的氧化还原态是否可用于调节金中心的路易斯酸度和催化性能，这一想法正在通过研究进行测试。总而言之，该研究项目有助于验证膦与锑中心结合的配体除了有助于构建新型氧化还原响应催化剂之外。为了对不同的学生群体进行教育，该项目允许主要研究者继续参与涉及 K-6 学生的各种服务和外展活动。一系列具有两亲性配体的金络合物，其中含有研究了作为 β-供体的膦和作为 β-受体的锑原子，最终目标是了解锑原子的氧化还原态是否可用于调节金的路易斯酸度和催化性能中心正在通过研究具有单（膦基）锑和双（膦基）锑配体的金配合物来测试这两种类型的配合物。锑原子从+III态到+V态的氧化预计会激活金中心并增强其对包括炔烃在内的路易斯碱性底物的亲和力。单(膦基)锑衍生物被设计为通过金的夺取而发生激活。通过邻近的路易斯酸性锑中心与卤化物配体结合预计以双(膦基)锑配体为特征的配合物的活化是通过直接形成而发生的。对于这两个络合物家族，金中心的活化程度源自其路易斯酸度的实验测定，以及其催化涉及炔烃的反应的能力。该项目的基本概念是可以操纵锑配体的氧化还原态作为调整辅助配体附近的过渡金属中心的反应性的手段，这些基本进展可能会在以下领域带来变革。氧化还原响应配体，在传感和催化方面的应用该项目的另一个重要成果是多元化学生群体的参与和教育。该教育计划还包括对西班牙/英语 K-6 双语课程的学生进行宣传。当地的小学和中学。