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

这一国际化学合作奖由无机化学、生物无机化学和有机金属化学计划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教授开展稳定卡宾的基础/基础研究。这些新型的卡宾被用于稳定高活性物种和激活稳定的分子。卡宾稳定的单原子和双原子碳(0)化合物的合成正在研究中。这些化合物在生物学和合成化学中具有相当重要的意义。正在开发使用卡宾来激活P4的合成循环，以及随后在随后的高活性单原子和双原子磷物种中添加有机碎片。事实上，为了满足日益严格的环境法规对磷衍生品日益增长的需求，使用白磷但避免使用氯的工艺是非常可取的。卡宾诱导的含BNH聚合物的解聚也在研究中。将氨硼烷作为燃料电池汽车的储氢材料实际应用的最大技术障碍是从脱氢过程中形成的聚合物中发现节能的再生途径。伯特朗教授的德国合作者、菲利普斯大学马尔堡分校的格诺特·弗伦金教授正在进行精确描述这些新化合物的计算。这项德国工作由德国金融研究基金会(DFG)单独支持。该项目处于有机化学、无机化学和物理化学的交界处，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小组的研究生有机会通过为期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，例如具有潜在生物应用的物质的研究(对苯炔)、对环境友好的大宗化学品的合成(磷衍生物)以及氢经济(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).