RUI: Selective C-H and C-X Bond Activation to Platinum(II) and Reactivity of the Cyclometalated Complexes

在这个由化学系化学结构、动力学和机理项目资助的RUI项目中，克雷格M。巴德学院的安德森将研究配体结构对铂中心活化碳氢键的选择性的影响。 他将研究选择性碳氢活化作为配体的功能，作为增加对所需产物的控制和改进工艺的策略，因为碳氢活化在催化等商业应用中具有实际意义。 具体来说，他计划合成各种萘基和菲基官能化亚胺配体，以促进和/或驱动铂（II）中心介导的C-H键的区域选择性。 新形成的环化铂络合物将被表征和研究其反应性。 配体将被设计成使得诸如所形成的铂配体的环尺寸、被激活的C-H键的键杂化以及所形成的环的芳香性等变量可以被详细检查。 将研究所得的环化产物，以研究影响还原消除产生C-C偶联的因素以及它们与各种底物的反应性。这项工作的一个重要组成部分是，它将涉及各级本科生研究人员。 这包括配体和配合物的多步合成，通过IR，UV/维斯，发射光谱，NMR和XRD（X射线衍射）对中间体和产物进行表征，以及使用计算技术来确定动力学和化学上有利的产物，以将理论与实验结果相关联。 拟议的研究计划，以建立一个更大的选择性准则（特别是在几个变量同时竞争的情况下），提供更有选择性的催化过程的发展的承诺，并有助于这些过程的亲密机制的理解。 通过金属络合物活化碳-氢键在将可用的原料官能化为更有用的产物和材料中是重要的，并且在合成领域例如在碳-碳键偶联中是密切相关的。

In this RUI project funded by the Chemical Structure, Dynamics and Mechanisms Program of the Chemistry Division, Professor Craig M. Anderson of Bard College will investigate the effect that ligand architecture has on the selectivity of carbon-hydrogen bond activation by platinum centers. He will examine selective carbon-hydrogen activation as a function of the ligand as a strategy for increasing control of desired products and improving processes as C-H activation has practical significance in commercial applications such as catalysis. Specifically, he plans to synthesize a variety of naphthyl and phenanthryl functionalized imine ligands in order to facilitate and/or drive the regioselectivity of C-H bonds mediated by platinum(II) centers. The newly formed cyclometalated platinum complexes will be characterized and studied for their reactivity. Ligands will be designed so that variables such as the ring size of the platinacycle formed, the bond hybridization of the C-H bond being activated, and aromaticity of the ring formed can be examined in detail. The resultant cyclometalated products will be studied in order to examine the factors affecting reductive elimination to produce C-C coupling as well as for their reactivity with various substrates.An important component of this work is that it will involve undergraduate student researchers at all levels. This includes the multi-step synthesis of ligands and complexes, the characterization of intermediates and products by IR, UV/Vis, emission spectroscopy, NMR, and XRD (X-ray diffraction) where possible, and the use of computational techniques to determine the kinetically and thermodynamically favored products in order to correlate theory with experimental results. The proposed research plans to establish a greater set of selectivity guidelines (especially in cases where several variables compete simultaneously), offer promise for the development of more selective catalytic processes, and contribute to the understanding of the intimate mechanisms of these processes. The activation of carbon-hydrogen bonds by metal complexes is important in the functionalization of available feedstocks into more useful products and materials, and is germane in the area of synthesis, for example, in carbon-carbon bond coupling.