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

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franois教授Gabbaï研究了将刘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。该项目的目标是确定锑中心的氧化还原状态是否可以用来调节金中心的路易斯酸度和催化性能。这一想法正通过研究配合物在炔烃亲电活化中的催化性能而得到验证。总之，这个研究项目有助于验证这样一个概念，即结合磷化氢和锑中心的配体可以用于构建新的氧化还原反应催化剂。除了为不同学生群体的教育做出贡献外，该项目还允许主要调查员参与涉及K-6学生的各种服务和推广活动。含膦的两亲性配体的一系列金配合物&amp；#963；-供体和一个锑原子作为研究的最终目的是了解锑原子的氧化还原状态是否可以用来调节金中心的路易斯酸度和催化性能。这个想法正在通过研究单（磷酸）锑和双（磷酸）锑配体的金配合物来验证。对于这两种类型的配合物，锑原子从+III态氧化到+V态有望激活金中心，并增强其对刘易斯碱底物（包括炔烃）的亲和力。单（磷）锑衍生物的设计是这样的，激活发生在金结合的卤化物配体被邻近的刘易斯酸性锑中心抽离。以双（膦）锑配体为特征的配合物的活化预计通过形成直接的Au&amp；某人的互动。对于这两个家族的配合物，金中心所经历的活化程度是由它的刘易斯酸度的实验测定得来的，以及它催化涉及炔的反应的能力。这个项目的核心是一个基本的概念，即锑配体的氧化还原状态可以被操纵，作为一种调节由辅助配体保持的过渡金属中心的反应性的手段。这些基本进展可能在氧化还原反应配体领域具有变革性，并在传感和催化方面得到应用。这个项目的另一个重要成果是不同学生群体的参与和教育。该教育计划还包括向在当地小学和中学就读西班牙语/英语K-6双语班的学生提供服务。

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.