Small Molecule Activation and Coordination Chemistry

小分子活化与配位化学

• 批准号: 0415506
• 负责人: Peter Wolczanski
• 金额: $ 54万
• 依托单位: Cornell University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2004
• 资助国家: 美国
• 起止时间: 2004-08-01 至 2007-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0415506&HistoricalAwards=false
• 关键词: Small; Molecule; Activation; Coordination; Chemistry

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.

康奈尔大学化学系的Peter Wolczanski博士得到化学系无机，生物无机和有机化学计划的支持，研究过渡金属对小分子的活化作用。d2过渡金属的反应路径可以定义为对称或反对称的轨道，并且它们的自旋状态可以被评估为单线态或三线态。利用这些原理，我们将研究三个配位的第5和第6族分子的反应模式，以及各种电子态的影响。高级量子计算将被用来解释化学反应性，并揭示可用于预测其对小分子的反应性的基本原理。此外，基于[YMX]n的聚集体将在其磁性和反应性方面进行研究。当Y = tBu3SiS和X =卤化物时，单元的空间不对称性表现为形成12元轮，其中金属中心之间的磁耦合是反铁磁的。最后，R2R'SiCCSiR2R'型空间大体积炔将作为辅助配体应用于烯烃催化体系，包括聚合反应。该项目将对决定重要分子类别化学反应性的潜在因素有新的认识。此外，还将准备在纳米磁学中具有重要意义的系统，这些系统可能用作纳米计算材料。将寻找重要工业过程的催化剂。该项目的教育目标包括培养独立、多才多艺的博士、博士后和本科生。