American Chemical Society
ja9b13571_si_007.cif (605.11 kB)

Coupling of Nitric Oxide and Release of Nitrous Oxide from Rare-Earth-Dinitrosyliron Complexes

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posted on 2020-02-20, 13:51 authored by Arun Kumar Bar, María José Heras Ojea, Jinkui Tang, Richard A. Layfield
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.