Molybdenum‐Mediated N(2)‐Splitting and Functionalization in the Presence of a Coordinated Alkyne

A new [PCCP]‐coordinated molybdenum platform comprising a coordinated alkyne was employed for the cleavage of molecular dinitrogen. The coordinated η (2)‐alkyne was left unaffected during this reduction. DFT calculations suggest that the reaction proceeds via an initially generated terminal N(2)‐complex, which is converted to a dinuclear μ‐(η (1):η (1))‐N(2)‐bridged intermediate prior to N−N bond cleavage. Protonation, alkylation and acylation of the resulting molybdenum nitrido complex led to the corresponding N‐functionalized imido complexes. Upon oxidation of the N‐acylated imido derivative in MeCN, a fumaronitrile fragment was built up via C−C coupling of MeCN to afford a dinuclear molybdenum complex. The key finding that the strong N≡N bond may be cleaved in the presence of a weaker, but spatially constrained C≡C bond contradicts the widespread paradigm that coordinated alkynes are in general more reactive than gaseous N(2).