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

无机化学、生物无机化学和金属有机化学项目的这一奖项支持罗格斯大学艾伦·S·戈德曼教授的实验室研究，以开发将在C-H键上进行光化学官能化的催化剂。碳氢化合物的这种光化作用是建立在对其发生的化学机制的不断加深的理解基础上的。我们将研究具有代表性的催化剂的动力学、热力学和分子轨道转化。这些体系基于可溶的后过渡金属络合物，由于它们在相关的催化过程中的成功，特别是工业氢甲酰化过程的成功，以及它们独特的区域选择性，因此是很有前途的。此外，还将研究醛脱甲基化这一反转反应，因为它是羰化反应的微观反转反应，而且具有重要的潜在价值。有效地将世界上主要的含碳资源，如煤炭、天然气和石油，转化为商品化学品和低污染燃料，对于一个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的过程在化学上很困难，在经济上也很重要，这一过程将使用戈德曼博士实验室开发的新型光化学催化剂进行。这些催化剂的发展取决于我们进一步了解催化剂在分子水平上是如何工作的。通过一系列系统的动力学和热力学实验，结合理论计算，探讨了光化学羰化反应的机理。

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.