Department of Chemistry, Princeton University, Frick Laboratory 292, Princeton, 08544 (USA).
Angew Chem Int Ed Engl. 2014 Dec 15;53(51):14211-5. doi: 10.1002/anie.201408725. Epub 2014 Oct 16.
The bis(imino)pyridine 2,6-(2,6-iPr2-C6H3N=CPh)2-C5H3N ((iPr)BPDI) molybdenum dinitrogen complex, [{((iPr)BPDI)Mo(N2)}2(μ2,η(1),η(1)-N2)] has been prepared and contains both weakly (terminal) and modestly (bridging) activated N2 ligands. Addition of ammonia resulted in sequential N-H bond activations, thus forming bridging parent imido (μ-NH) ligands with concomitant reduction of one of the imines of the supporting chelate. Using primary and secondary amines, model intermediates have been isolated that highlight the role of metal-ligand cooperativity in NH3 oxidation.
双(亚氨基)吡啶 2,6-(2,6-异丙基-2-苯基-C6H3N=CPh)2-C5H3N((iPr)BPDI)钼二氮配合物，[{((iPr)BPDI)Mo(N2)}2(μ2,η(1),η(1)-N2)]，已经被制备出来，并且含有弱(末端)和适度(桥接)活化的 N2 配体。添加氨导致了顺序的 N-H 键活化，从而形成了桥接的原始亚氨基(μ-NH)配体，同时还原了配位螯合物的一个亚胺。使用伯胺和仲胺，已经分离出模型中间体，突出了金属-配体协同作用在 NH3 氧化中的作用。
