Small Molecule Activation and Coordination Chemistry

Peter Wolczanski博士，康奈尔大学化学系，由化学部无机化学、生物无机化学和有机金属化学项目支持，研究过渡金属对小分子的激活作用。D2过渡金属的反应轨道可定义为对称或反对称，其自旋态可定义为单重态或三重态。利用这些原理，我们将研究三个配位基团5和6的分子在不同电子态影响下的反应模式。高水平的量子计算将被用来解释化学反应性，并揭示可以用来预测它们对小分子的反应性的潜在原理。此外，还将研究基于[YMX]n的聚集体的磁性和反应活性。当Y=tBu3SiS和X=卤化物时，单元的空间不对称性表现为12元轮子的形成，其中金属中心之间的磁耦合是反铁磁性的。最后，R2R‘SiCCSiR2R’类型的空间大小的炔烃将作为辅助配体应用于包括聚合在内的烯烃催化体系中。该项目将对决定重要分子的化学反应活性的潜在因素有新的理解。此外，还将准备在纳米磁学中具有重要意义的系统，并可能将其应用于纳米计算材料。将寻求用于重要工业过程的催化剂。该项目的教育目标包括独立、多才多艺的博士、博士后助理和本科生的教育。

Dr. Peter Wolczanski, Chemistry Department, Cornell University, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division for research into small molecule activation by transition metals. The reaction pathways of d2 transition metals can be orbitally defined as symmetric or antisymmetric, and their spin states can be assessed as singlet or triplet. Using these principles, the reactivity patterns of three coordinate group 5 and 6 molecules will be studied with respect to the influence of various electronic states. High level quantum calculations will be employed to interpret the chemical reactivity and to uncover underlying principles that can be used to predict their reactivity toward small molecules. In addition, aggregates based on [YMX]n will be studied in terms of their magnetic properties, and their reactivity. When Y = tBu3SiS and X = halide, the steric asymmetry of the unit is manifested in the formation of 12-membered wheels, where the magnetic coupling between metal centers is antiferromagnetic. Finally, sterically bulky alkynes of the type R2R'SiCCSiR2R' will be applied as ancillary ligands in systems aimed at olefin catalysis, including polymerizations.This project will develop new understanding of the underlying factors that determine the chemical reactivity of important classes of molecules. In addition systems will be prepared that are of importance in nanomagnetics with possible applications as nanocomputing materials. Catalysts for important industrial processes will be sought. The educational objective of this project includes the education of independent, versatile PhDs, postdoctoral associates and undergraduates.