Catalytic Hydrocarbon Carbonylation and Aldehyde Decarbonylation: The Design of Soluble Transition-Metal Based Systems

该无机、生物无机和有机金属化学项目奖项支持罗格斯大学 Alan S. Goldman 教授实验室的研究，以开发可在 C-H 键上进行光化学功能化的催化剂。 碳氢化合物的这种光化学羰基化作用是基于对其发生的化学机制的深入了解。 将研究代表性催化剂的动力学、热力学和分子轨道变换。 系统基于可溶性后过渡金属配合物，由于其在相关催化过程（特别是工业加氢甲酰化过程）中的成功及其不寻常的区域选择性，因此前景广阔。 逆反应，醛脱羰，也将被研究，因为它是羰基化的微观逆反应，也具有重要的潜在价值。 有效地将世界主要含碳资源（例如煤炭、天然气和石油）转化为商品化学品和低污染燃料对于繁荣的经济至关重要。 通过激活稳定的C-H键来添加有机官能团这一化学上困难且经济上重要的过程将使用Goldman博士实验室开发的新型光化学催化剂来进行。 这些催化剂的开发取决于进一步了解催化剂如何在分子水平上发挥作用。 光化学羰基化的机理将通过一系列系统的动力学和热力学实验以及理论计算来探讨。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry Program supports research in the laboratory of Professor Alan S. Goldman of Rutgers University to develop catalysts that will photochemically functionalize at C-H bonds. This photochemical carbonylation of hydrocarbons is based on a developing understanding of the chemical mechanisms whereby it occurs. Representative catalysts will be studied as to their kinetics, thermodynamics, and molecular orbital transformations. Systems are based on soluble late transition-metal complexes, which are promising because of their success in related catalytic processes, particularly industrial hydroformylation processes, and their unusual regioselectivity. The reverse reaction, aldehyde decarbonylation, will also be studied as it is the microscopic reverse of carbonylation and also of significant potential value. Efficiently turning the world's major carbon-containing resources, such as coal, natural gas and petroleum, into commodity chemicals and low pollution fuels is essential to a thriving economy. The chemically difficult and economically important process of adding organic functionality by activating stable C-H bonds will be undertaken using new photochemical catalysts developed in Dr. Goldman's laboratory. The development of these catalysts depends on furthering our understanding of how the catalysts work at a molecular level. The mechanism of photochemical carbonylation is to be probed in a systematic series of kinetic and thermodynamic experiments coupled with theoretical calculations.