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Coordination chemistry from trigonally coordinated iron platforms: Chemistry relevant to dinitrogen reduction

Betley, Theodore A. and Peters, Jonas C. (2005) Coordination chemistry from trigonally coordinated iron platforms: Chemistry relevant to dinitrogen reduction. Abstracts of Papers of the American Chemical Society, 230 . INOR 80. ISSN 0065-7727.

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Use of the sterically-encumbering tris(phosphino)borate ligand, 1;PhB(CH_2P^iPr_2)_33;-, enabled isolation of tetrahedral iron species spanning five oxidn. states, all featuring nitrogenous ligands in the fourth coordination site. Low oxidn. state iron species (e.g. Fe^0, Fe^I) readily bind weakly-coordinating, π-acidic ligands (e.g. N_2). The bound dinitrogen can then be further reduced and even functionalized to yield diazenido products (e.g. Fe^(II)(N_2R)). High oxidn. state iron complexes were fashioned through oxidative group transfer reactions to yield imido/nitrene products (e.g. Fe^(III)(NR)), while decompn. of an iron-ligated, dibenzoazabicycloheptadiene amide yielded a room temp. stable Fe^(IV) nitride complex. The ability to mediate multi-electron redox transformations demonstrates the redox flexibility inherent to these iron complexes. We have demonstrated that a singular iron site is capable of stabilizing the span of oxidn. states required for dinitrogen redn. (i.e., Fe^I in Fe(N_2) and Fe^(IV) in Fe≡N) and have isolated and characterized several of the potential intermediates relevant to dinitrogen redn.

Item Type:Article
Peters, Jonas C.0000-0002-6610-4414
Additional Information:© 2005 American Chemical Society.
Record Number:CaltechAUTHORS:20140729-085417639
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:47549
Deposited By: Tony Diaz
Deposited On:29 Jul 2014 18:15
Last Modified:26 Nov 2019 11:15

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