Coupling of nitric oxide and release of nitrous oxide from rare-earth-dinitrosyliron complexes

Bar, Arun Kumar and Heras Ojea, María José and Tang, Jinkui and Layfield, Richard A. (2020) Coupling of nitric oxide and release of nitrous oxide from rare-earth-dinitrosyliron complexes. Journal of the American Chemical Society, 142 (9). 4104–4107. ISSN 0002-7863 (https://doi.org/10.1021/jacs.9b13571)

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Abstract

Addition of Lewis acidic [Cp*2M]+ (M = Y, Gd) to the dinitrosyliron complexes (DNICs) [(NacNacAr)Fe(NO)2]− (Ar = mesityl, 2,6-diisopropylphenyl) results in formation of the isonitrosyl-bridged DNICs [(Cp*)2M(μ-ON)2Fe(NacNacAr)]. When Ar = 2,6-diisopropylphenyl, coupling of the NO ligands and release of N2O occur. Two factors contribute to this previously unobserved DNIC reactivity mode. First, the oxophilic rare-earth elements drive the formation of isonitrosyl bonds, forcing the DNIC nitrogen atoms into proximity. Second, the bulky substituents further squeeze the DNIC, which ultimately overcomes the barrier to NO coupling, demonstrating that N2O elimination can occur from a single iron center.