Well-defined, bimetallic molecular clefts: A new approach to nitrogen fixation and transformation

一种新的大环支架已经开发出来，这将有助于建设创新的金属分子，其中直接环境和并列的金属是由设计定义。这些化合物采用的铰链或Pacman拓扑结构将有助于通过提供明确定义和易于研究的反应袋来促进科学上独特的和潜在的商业上可利用的氮化学。首先，将考虑用于二氮转化的新的、低价的、早期过渡金属（钛、锆、钒、镧系元素）Pacman化合物的制备和表征。这是一种原始的、预制的双核方法来活化二氮，并将产生非碎片化合物，这些化合物被引发与有机底物反应以形成新的N-E键（E = H、C、Si）。这些新化合物的反应性将通过明智地选择金属和合理地修饰配体外围来控制。氢化，甲硅烷基化，环加成和N-原子转移反应将被评估为化学计量和催化路线，将二氮衍生的N到有机底物。

A new macrocyclic scaffold has been developed that will assist in the construction of innovative bimetallic molecules where both the immediate environment and juxtaposition of the metals are defined by design. The hinged, or Pacman topology that these compounds adopt will help promote scientifically unique and potentially commercially exploitable chemistry of nitrogen by providing a well-defined and easily-studied reaction pocket. Initially, the preparation and characterisation of new, low valent, early transition metal (titanium, zirconium, vanadium, lanthanides) Pacman compounds for dinitrogen transformation will be considered. This is an original, prefabricated dinuclear approach to dinitrogen activation and will yield nonfragmentary compounds that are primed to react with organic substrates to form new N-E bonds (E = H, C, Si). The reactivity of these novel compounds will be controlled by judicious choice of metal and reasoned modification of the ligand periphery. Hydrogenation, silylation, cycloaddition and N-atom transfer reactions will be evaluated as stoichiometric and catalytic routes to the incorporation of dinitrogen-derived N into organic substrates.