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.

在化学司的化学合成计划的支持下，得克萨斯州A＆M大学化学系的FrançoisGabbaï教授介绍了磷酸化的化学综合体，该化学融合了Lewis酸性抗量原子作为配体建筑的一部分。该项目的目的是确定锑中心的氧化还原状态是​​否可用于调节金中心的刘易斯酸度和催化特性。通过研究醇的亲电激活中复合物的催化特性来测试这个想法。总的来说，该研究计划有助于验证通知，即配体将磷酸与锑中心结合在一起，可用于构建新型的氧化还原响应性催化剂。除了为一群学生的教育做出贡献之外，该项目还允许主要研究者保持他参与涉及K-6学生的各种服务和外展活动。一系列具有弹药型配体的黄金综合体，其中包含含磷的含量为phosphins，并在含有磷酸盐的最终范围内，以及是否符合positiate arton artimiment＆＃963; -dyantious atom and Atoc ate​​ Ats Atom Ats At＆＃963; - ＆＃963；锑原子的氧化还原状态可用于调节黄金中心的刘易斯酸度和催化特性。通过研究具有单次（磷）锑和二（磷）锑配体的黄金复合物来测试这个想法。对于两种类型的复合物，从 +III到 +V状态的锑原子的氧化预计将激活黄金中心，并增强其对包括酗酒在内的Lewis基本底物的亲和力。设计了单声道（磷）锑衍生物，以至于激活是通过相邻的刘易斯酸性锑中心抽象通过将金色的卤化物配体抽象出现的。有望通过形成直接的Au＆＃8594; SB相互作用来激活具有双（磷）锑配体的复合物。对于两个复合物的家族，黄金中心所经历的激活程度均来自其刘易斯酸度的实验性确定，以及其催化涉及反应的能力。该项目的核心是基本观念，即可以操纵锑配体的氧化还原状态，作为调整辅助配体靠近过渡金属中心的反应性的一种手段。这些基本进步可能在氧化还原响应配体领域具有变革性，并在敏感性和催化中应用。该项目的另一个重要结果是潜水员群体的参与和教育。该教育计划还包括向当地小学和中级学校参加西班牙语/英语K-6双语言课的学生的宣传。