Formation of the N≡N Triple Bond from Reductive Coupling of a Paramagnetic Diruthenium Nitrido Compound

化学 三键 顺磁性 联轴节(管道) 药物化学 立体化学 双键 高分子化学 凝聚态物理 机械工程 物理 工程类
作者
Sungho V. Park,Amanda R. Corcos,Alexander N. Jambor,Tzuhsiung Yang,John F. Berry
出处
期刊:Journal of the American Chemical Society [American Chemical Society]
卷期号:144 (7): 3259-3268 被引量:12
标识
DOI:10.1021/jacs.1c13396
摘要

Construction of nitrogen–nitrogen triple bonds via homocoupling of metal nitrides is an important fundamental reaction relevant to a potential Nitrogen Economy. Here, we report that room temperature photolysis of Ru2(chp)4N3 (chp– = 2-chloro-6-hydroxypyridinate) in CH2Cl2 produces N2 via reductive coupling of Ru2(chp)4N nitrido species. Computational analysis reveals that the nitride coupling transition state (TS) features an out-of-plane "zigzag" geometry instead of the anticipated planar zigzag TS. However, with intentional exclusion of dispersion correction, the planar zigzag TS geometry can also be found. Both the out-of-plane and planar zigzag TS geometries feature two important types of orbital interactions: (1) donor–acceptor interactions involving intermolecular donation of a nitride lone pair into an empty Ru–N π* orbital and (2) Ru–N π to Ru–N π* interactions derived from coupling of nitridyl radicals. The relative importance of these two interactions is quantified both at and after the TS. Our analysis shows that both interactions are important for the formation of the N–N σ bond, while radical coupling interactions dominate the formation of N–N π bonds. Comparison is made to isoelectronic Ru2-oxo compounds. Formation of an O–O bond via bimolecular oxo coupling is not observed experimentally and is calculated to have a much higher TS energy. The major difference between the nitrido and oxo systems stems from an extremely large driving force, ∼−500 kJ/mol, for N–N coupling vs a more modest driving force for O–O coupling, −40 to −140 kJ/mol.
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