Effects of N Binding Mode on Iron-Based Functionalization of Dinitrogen to Form an Iron(III) Hydrazido Complex

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2018 Jun 30

PMID 29957940

Citations 12

Authors

Sean F McWilliams

Eckhard Bill

Gudrun Lukat-Rodgers

Kenton R Rodgers

Brandon Q Mercado

Patrick L Holland

Affiliations

Soon will be listed here.

Abstract

Distinguishing the reactivity differences between N complexes having different binding modes is crucial for the design of effective N-functionalizing reactions. Here, we compare the reactions of a K-bridged, dinuclear FeNNFe complex with a monomeric Fe(N) complex where the bimetallic core is broken up by the addition of chelating agents. The new anionic iron(0) dinitrogen complex has enhanced electron density at the distal N atoms of coordinated N, and though the N is not as weakened in this monomeric compound, it is much more reactive toward silylation by (CH)SiI (TMSI). Double silylation of N gives a three-coordinate iron(III) hydrazido(2-) complex, which is finely balanced between coexisting S = 1/2 and S = 3/2 states that are characterized by crystallography, spectroscopy, and computations. These results give insight into the interdependence between binding modes, alkali dependence, reactivity, and magnetic properties within an iron system that functionalizes N.

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