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

一种新的大环支架已经被开发出来，它将有助于创新双金属分子的构建，其中金属的直接环境和并置都是由设计定义的。这些化合物采用的铰链或吃豆人拓扑结构将通过提供一个定义明确且易于研究的反应袋，有助于促进科学上独特的氮化学和潜在的商业开发。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、预制的双氮活化方法，将产生非碎片化合物，这些化合物与有机底物反应形成新的N-E键（E = H， C, Si）。这些新化合物的反应性将通过合理的金属选择和配体外围的合理修饰来控制。氢化、硅基化、环加成和N原子转移反应将被评价为二氮衍生的N进入有机底物的化学计量学和催化途径。

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.