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Effects of N

Authors :
Sean F, McWilliams
Eckhard, Bill
Gudrun, Lukat-Rodgers
Kenton R, Rodgers
Brandon Q, Mercado
Patrick L, Holland
Source :
Journal of the American Chemical Society. 140(27)
Publication Year :
2018

Abstract

Distinguishing the reactivity differences between N(2) complexes having different binding modes is crucial for the design of effective N(2) functionalizing reactions. Here, we compare the reactions of a K-bridged, dinuclear FeNNFe complex with a monomeric Fe(N(2)) 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(2), and though the N(2) is not as weakened in this monomeric compound, it is much more reactive toward silylation by TMSI. Double silylation of N(2) 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(2).

Details

ISSN :
15205126
Volume :
140
Issue :
27
Database :
OpenAIRE
Journal :
Journal of the American Chemical Society
Accession number :
edsair.pmid..........a88283e8ded16b181d32e802cd39354f