Fluorinated Closo-Heteroborane Anions and Nonclassical Metal Carbonyls

科罗拉多州立大学化学系Steven H.Strauss博士受到化学部无机、生物无机和有机金属项目的支持，致力于研究氟化稠杂硼阴离子作为弱配位阴离子(WCA)的使用以及非经典金属羰基的研究。含氟杂硼阴离子将作为一组新的WCA被开发出来，这些WCA在各种条件下都是稳定的，包括高温和酸碱水溶液。这些阴离子将相对便宜，易于制备，并将被应用于各种问题，包括结构和成键，材料科学，和催化。WCA将与阳离子金属羰基一起用作反离子，这些阳离子很少或根本没有金属配体pi的反键。将研究这些络合物的结构、成键和化学反应活性，并将开发应用，包括Diels-Alder和Michael加成催化和聚合物共混物中的锂离子电导。许多重要的实验室和工业过程都是由金属催化剂推动的。这项研究的中心是一类化合物，其中含有正电荷的金属碎片(称为阳离子)被与金属不强相互作用的大负电荷物种(称为弱配位阴离子或WCA)所抵消。由于阳离子金属-WCA络合物被认为是各种反应的良好催化剂，本项目将研究的新WCA是重要的，因为它们在实际应用中遇到的苛刻条件下将是廉价和稳定的。这些化合物可用于一些重要的工业过程，包括气体净化、水煤气变换催化和甲醇合成催化。一个将被研究的特殊应用是铜(I)催化的有机化合物在均相溶液中的羰基化反应。

Dr. Steven H. Strauss, Department of Chemistry, Colorado State University, is supported by the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division for research into the use of fluorinated closo-heteroborane anions as weakly coordinating anions (WCAs) and for investigations into nonclassical metal carbonyls. Fluorinated closo-heteroborane anions will be developed as a new set of WCAs that are stable under a wide variety of conditions, including high temperatures and in aqueous acid and base solutions. These anions will be relatively inexpensive and easy to prepare and will be applied to a variety of problems involving structure and bonding, materials science, and catalysis. The WCAs will be used as counterions with cationic metal carbonyls that possess little or no metal-ligand pi backbonding. The structure, bonding, and chemical reactivity of these complexes will be studied and applications, including Diels-Alder and Michael addition catalysis and lithium ion conductivity in polymer blends, will be developed. Many important laboratory and industrial processes are facilitated by metal catalysts. This research centers about a class of compounds in which a positively charged metal containing fragment (called a cation) is counterbalanced by a large negatively charged species that does not interact strongly with the metal (These are termed weakly coordinating anions or WCAs.). Since cationic metal-WCA complexes are known to be good catalysts for a variety of reactions, the new WCAs, to be studied in this project, are important because they will be inexpensive and stable under the harsh conditions encountered in real world application. Some of the important industrial processes in which these compounds may be used include gas purification, water gas shift catalysis, and methanol synthesis catalysis. A particular application that will be studied is the Cu(I)-catalyzed carbonylation of organic compounds in homogeneous solution.