Manganese nitride complexes in oxidation states III, IV, and V: synthesis and electronic structure

Henning Kropp; Amanda E King; Marat M Khusniyarov; Frank W Heinemann; Kyle M Lancaster; Serena DeBeer; Eckhard Bill; Karsten Meyer

doi:10.1021/ja306647c

Manganese nitride complexes in oxidation states III, IV, and V: synthesis and electronic structure

J Am Chem Soc. 2012 Sep 19;134(37):15538-44. doi: 10.1021/ja306647c. Epub 2012 Sep 6.

Authors

Henning Kropp¹, Amanda E King, Marat M Khusniyarov, Frank W Heinemann, Kyle M Lancaster, Serena DeBeer, Eckhard Bill, Karsten Meyer

Affiliation

¹ Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander University of Erlangen-Nuremberg, Egerlandstrasse 1, Erlangen, Germany.

PMID: 22920682
DOI: 10.1021/ja306647c

Abstract

The synthesis and characterization of a series of manganese nitrides in a tripodal chelating tris(carbene) ligand framework is described. Photolysis of [(TIMEN(xyl))Mn(N(3))](+) (where TIMEN(xyl) = tris[2-(3-xylylimidazol-2-ylidene)ethyl]amine) yields the isolable molecular Mn(IV) nitride, [(TIMEN(xyl))Mn(N)](+). Spectroscopic and DFT studies indicate that this Mn(IV) d(3) complex has a doublet electronic ground state. The metal-centered one-electron oxidation of this Mn(IV) species results in formation of the pentavalent Mn(V) nitride, [(TIMEN(xyl))Mn(N)](2+). Unlike previously reported, tetragonal Mn(V) nitrides with a d(2), nonmagnetic S = 0 ground state, this trigonal bipyramidal complex has a triplet ground state S = 1. One-electron reduction of [(TIMEN(xyl))Mn(N)](+) produces the neutral, nonmagnetic trivalent [(TIMEN(xyl))Mn(N)] species with a d(4) low-spin, S = 0, ground state.

Publication types

Research Support, N.I.H., Extramural
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

Electrons
Manganese / chemistry*
Models, Molecular
Oxidation-Reduction

Substances

Manganese