Metal–Metal Interactions in C3-Symmetric Diiron Imido Complexes Linked by Phosphinoamide Ligands

Subramaniam Kuppuswamy; Tamara M Powers; Bruce M Johnson; Mark W Bezpalko; Carl K Brozek; Bruce M Foxman; Louise A Berben; Christine M Thomas

doi:10.1021/ic302108k

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Metal–Metal Interactions in C3-Symmetric Diiron Imido Complexes Linked by Phosphinoamide Ligands

Journal article

Peer reviewed

Metal–Metal Interactions in C3-Symmetric Diiron Imido Complexes Linked by Phosphinoamide Ligands

Subramaniam Kuppuswamy, Tamara M Powers, Bruce M Johnson, Mark W Bezpalko, Carl K Brozek, Bruce M Foxman, Louise A Berben and Christine M Thomas

Inorganic chemistry, Vol.52(9), pp.4802-4811

05/06/2013

DOI: https://doi.org/10.1021/ic302108k

PMID: 23259457

Abstract

Redox reactions

Diirons

Reactivity

Ligands

Quantum Mechanics

The tris(phosphinoamide)-bridged FeIIFeII diiron complex Fe(μ-iPrNPPh2)3Fe(η2-iPrNPPh2) (1) can be reduced in the absence or presence of PMe3 to generate the mixed-valence FeIIFeI complexes Fe(μ-iPrNPPh2)3Fe(PPh2NHiPr) (2) or Fe(μ-iPrNPPh2)3Fe(PMe3) (3), respectively. Following a typical oxidative group transfer procedure, treatment of 2 or 3 with organic azides generates the mixed-valent FeIIFeIII imido complexes Fe(iPrNPPh2)3Fe≡NR (R = tBu (4), Ad (5), 2,4,6-trimethylphenyl (6)). These complexes represent the first examples of first-row bimetallic complexes featuring both metal–ligand multiple bonds and metal–metal bonds. The reduced complexes 2 and 3 and imido complexes 4–6 have been characterized via X-ray crystallography, Mössbauer spectroscopy, cyclic voltammetry, and SQUID magnetometry, and a theoretical description of the bonding within these diiron complexes has been obtained using computational methods. The effect of the metal–metal interaction on the electronic structure and bonding in diiron imido complexes 4–6 is discussed in the context of similar monometallic iron imido complexes.

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Title: Metal–Metal Interactions in C3-Symmetric Diiron Imido Complexes Linked by Phosphinoamide Ligands
Creators: Subramaniam Kuppuswamy - Department of Chemistry, Brandeis University, 415 South Street MS 015, Waltham, Massachusetts 02454, United States
Tamara M Powers - Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02139, United States
Bruce M Johnson - Department of Chemistry, University of California—Davis, Davis, California 95616, United States
Mark W Bezpalko - Department of Chemistry, Brandeis University, 415 South Street MS 015, Waltham, Massachusetts 02454, United States
Carl K Brozek - Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, United States
Bruce M Foxman - Department of Chemistry, Brandeis University, 415 South Street MS 015, Waltham, Massachusetts 02454, United States
Louise A Berben - Department of Chemistry, University of California—Davis, Davis, California 95616, United States
Christine M Thomas - Department of Chemistry, Brandeis University, 415 South Street MS 015, Waltham, Massachusetts 02454, United States
Publication Details: Inorganic chemistry, Vol.52(9), pp.4802-4811
Identifiers: 9923989575701921
Academic Unit: Department of Chemistry
Language: English
Resource Type: Journal article

Metal–Metal Interactions in C3-Symmetric Diiron Imido Complexes Linked by Phosphinoamide Ligands

Abstract

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