International Collaboration in Chemistry: Carbenes as Stabilizing and Activating Agents in Boron, Carbon and Phosphorus Chemistry

这个国际化学合作奖由无机、生物无机和有机金属化学项目和国际科学与工程办公室资助，支持加州大学河滨分校的Guy Bertrand教授开展关于稳定碳烯使用的基础研究。这些新型碳烯用于稳定高活性物质和激活稳定分子。研究了碳稳定的单原子和双原子碳(0)化合物的合成。这些化合物在生物学和合成化学中具有相当重要的意义。目前正在开发利用碳烯激活P4的合成循环，然后将有机片段添加到随后的高活性单原子和双原子磷物种中。事实上，在日益严格的环境法规下，使用白磷但不使用氯的工艺是非常理想的，以满足对磷衍生物日益增长的需求。含碳氢化合物的聚合物的碳诱导的去聚反应也在研究中。将氨硼烷作为燃料电池动力汽车的储氢材料进行实际应用的最大技术障碍在于发现脱氢过程中形成的聚合物的节能再生途径。Bertrand教授的德国合作者，来自马尔堡菲利普斯大学的Gernot Frenking教授正在进行精确描述这些新化合物的计算。德国的这项工作由德国研究协会（DFG）单独支持。这个项目是有机、无机和物理化学之间的界面，非常适合研究生同事的多学科教育。参与这项合作的美国和德国的研究生有机会通过三个月的互访学习计算和实验技术。该项目涉及对社会至关重要的几个问题，例如研究具有潜在生物应用的物质（对苯）、散装化学品的环境友好合成（磷衍生物）和氢经济（氨硼烷）。

This International Collaborations in Chemistry award funded by the Inorganic, Bioinorganic, and Organometallic Chemistry Program and the Office of International Science and Engineering supports work by Professor Guy Bertrand of the University of California at Riverside to carry out fundamental/basic studies on the use of stable carbenes. These novel carbenes are used for stabilizing highly reactive species and for activating stable molecules. The synthesis of carbene-stabilized monoatomic and diatomic carbon(0) compounds is being investigated. These compounds are of considerable importance in biology and in synthetic chemistry. Synthetic cycles using carbenes to activate P4 and the subsequent addition of organic fragments to the ensuing highly reactive mono- and diatomic phosphorus species are being developed. Indeed, processes using white phosphorus, but avoiding chlorine, are highly desirable to meet the growing demand for phosphorus derivatives under increasingly stringent environmental regulations. The carbene-induced de-oligomerization of BNH containing polymers also under investigation. The greatest technical barrier for a practical application of ammonia borane as a hydrogen-storage material for fuel-cell-powered vehicles lies in the discovery of energy-efficient regeneration routes from the polymers that are formed in the dehydrogenation process. Calculations to accurately describe these novel compounds are being performed by Professor Bertrand's German collaborator, Professor Gernot Frenking of Phillipps-Universitaet Marburg. This German work is separatately supported by the Deutsche Forschungsgemeinschaft (DFG). This project is at the interfaces between organic, inorganic, and physical chemistry and is well-suited for the multidisciplinary education of graduate coworkers. The graduate students of the U.S. and German groups involved in this collaborative effort have the opportunity to learn both computational and experimental techniques through reciprocal visits of three months. This project addresses several issues that are of critical importance for society, such as the study of substances with potential biological applications (para-benzynes), the environmentally friendly synthesis of bulk chemicals (phosphorus derivatives), and the hydrogen economy (ammoniaborane).