High-spin chloro mononuclear MnIII complexes: A multifrequency high-field EPR study

Claire Mantel, Hongyu Chen, Robert H. Crabtree, Gary W Brudvig, Jacques Pécaut, Marie Noëlle Collomb, Carole Duboc

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

The isolation, structural characterization, and electronic properties of two six-coordinated chloromanganese (III) complexes, [Mn(terpy)(Cl)3] (1) and [Mn(Phterpy)(Cl)3] (2), are reported (terpy=2,2′: 6′2″-terpyridine, Phterpy=4′-phenyl-2,2′:6′, 2″-terpyridine). These complexes complement a series of mononuclear azide and fluoride Mn(III) complexes synthesized with neutral N-tridentate ligands, [Mn(L)(X)3] (X=F- or N3- and L=terpy or bpea [N,N-bis(2-pyridylmethyl)-ethylamine)], previously described. Similar to these previous complexes, 1 and 2 exhibit a Jahn-Teller distortion of the octahedron, characteristic of a high-spin Mn(III) complex (S=2). The analysis of the crystallographic data shows that, in both cases, the manganese ion lies in the center of a distorted octahedron characterized by an elongation along the tetragonal axis. Their electronic properties were investigated by multifrequency EPR (190-475 GHz) performed in the solid state at different temperatures (5-15 K). This study confirms our previous results and further shows that: i) the sign of D is correlated with the nature of the tetragonal distortion; ii) the magnitude of D is not sensitive to the nature of the anions in our series of rhombic complexes, contrary to the porphyrinic systems; iii) the |E/D| values (0.124 for 1 and 0.085 for 2) are smaller compared to those found for the [Mn(L)(X)3] complexes (in the range of 0.146 to 0.234); and iv) the E term increases when the ligand-field strength of the equatorial ligands decreases.

Original languageEnglish
Pages (from-to)541-546
Number of pages6
JournalChemPhysChem
Volume6
Issue number3
DOIs
Publication statusPublished - Mar 2005

Fingerprint

Paramagnetic resonance
Ligands
Electronic properties
ligands
Jahn-Teller effect
manganese ions
Azides
Manganese
Fluorides
electronics
complement
elongation
Anions
fluorides
Elongation
field strength
isolation
Ions
anions
solid state

Keywords

  • Electronic properties
  • EPR spectroscopy
  • Manganese
  • Multifrequency EPR spectroscopy
  • N ligands

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Mantel, C., Chen, H., Crabtree, R. H., Brudvig, G. W., Pécaut, J., Collomb, M. N., & Duboc, C. (2005). High-spin chloro mononuclear MnIII complexes: A multifrequency high-field EPR study. ChemPhysChem, 6(3), 541-546. https://doi.org/10.1002/cphc.200400484

High-spin chloro mononuclear MnIII complexes : A multifrequency high-field EPR study. / Mantel, Claire; Chen, Hongyu; Crabtree, Robert H.; Brudvig, Gary W; Pécaut, Jacques; Collomb, Marie Noëlle; Duboc, Carole.

In: ChemPhysChem, Vol. 6, No. 3, 03.2005, p. 541-546.

Research output: Contribution to journalArticle

Mantel, C, Chen, H, Crabtree, RH, Brudvig, GW, Pécaut, J, Collomb, MN & Duboc, C 2005, 'High-spin chloro mononuclear MnIII complexes: A multifrequency high-field EPR study', ChemPhysChem, vol. 6, no. 3, pp. 541-546. https://doi.org/10.1002/cphc.200400484
Mantel, Claire ; Chen, Hongyu ; Crabtree, Robert H. ; Brudvig, Gary W ; Pécaut, Jacques ; Collomb, Marie Noëlle ; Duboc, Carole. / High-spin chloro mononuclear MnIII complexes : A multifrequency high-field EPR study. In: ChemPhysChem. 2005 ; Vol. 6, No. 3. pp. 541-546.
@article{a7cd602704074424a50e2cec7f59cf1d,
title = "High-spin chloro mononuclear MnIII complexes: A multifrequency high-field EPR study",
abstract = "The isolation, structural characterization, and electronic properties of two six-coordinated chloromanganese (III) complexes, [Mn(terpy)(Cl)3] (1) and [Mn(Phterpy)(Cl)3] (2), are reported (terpy=2,2′: 6′2″-terpyridine, Phterpy=4′-phenyl-2,2′:6′, 2″-terpyridine). These complexes complement a series of mononuclear azide and fluoride Mn(III) complexes synthesized with neutral N-tridentate ligands, [Mn(L)(X)3] (X=F- or N3- and L=terpy or bpea [N,N-bis(2-pyridylmethyl)-ethylamine)], previously described. Similar to these previous complexes, 1 and 2 exhibit a Jahn-Teller distortion of the octahedron, characteristic of a high-spin Mn(III) complex (S=2). The analysis of the crystallographic data shows that, in both cases, the manganese ion lies in the center of a distorted octahedron characterized by an elongation along the tetragonal axis. Their electronic properties were investigated by multifrequency EPR (190-475 GHz) performed in the solid state at different temperatures (5-15 K). This study confirms our previous results and further shows that: i) the sign of D is correlated with the nature of the tetragonal distortion; ii) the magnitude of D is not sensitive to the nature of the anions in our series of rhombic complexes, contrary to the porphyrinic systems; iii) the |E/D| values (0.124 for 1 and 0.085 for 2) are smaller compared to those found for the [Mn(L)(X)3] complexes (in the range of 0.146 to 0.234); and iv) the E term increases when the ligand-field strength of the equatorial ligands decreases.",
keywords = "Electronic properties, EPR spectroscopy, Manganese, Multifrequency EPR spectroscopy, N ligands",
author = "Claire Mantel and Hongyu Chen and Crabtree, {Robert H.} and Brudvig, {Gary W} and Jacques P{\'e}caut and Collomb, {Marie No{\"e}lle} and Carole Duboc",
year = "2005",
month = "3",
doi = "10.1002/cphc.200400484",
language = "English",
volume = "6",
pages = "541--546",
journal = "ChemPhysChem",
issn = "1439-4235",
publisher = "Wiley-VCH Verlag",
number = "3",

}

TY - JOUR

T1 - High-spin chloro mononuclear MnIII complexes

T2 - A multifrequency high-field EPR study

AU - Mantel, Claire

AU - Chen, Hongyu

AU - Crabtree, Robert H.

AU - Brudvig, Gary W

AU - Pécaut, Jacques

AU - Collomb, Marie Noëlle

AU - Duboc, Carole

PY - 2005/3

Y1 - 2005/3

N2 - The isolation, structural characterization, and electronic properties of two six-coordinated chloromanganese (III) complexes, [Mn(terpy)(Cl)3] (1) and [Mn(Phterpy)(Cl)3] (2), are reported (terpy=2,2′: 6′2″-terpyridine, Phterpy=4′-phenyl-2,2′:6′, 2″-terpyridine). These complexes complement a series of mononuclear azide and fluoride Mn(III) complexes synthesized with neutral N-tridentate ligands, [Mn(L)(X)3] (X=F- or N3- and L=terpy or bpea [N,N-bis(2-pyridylmethyl)-ethylamine)], previously described. Similar to these previous complexes, 1 and 2 exhibit a Jahn-Teller distortion of the octahedron, characteristic of a high-spin Mn(III) complex (S=2). The analysis of the crystallographic data shows that, in both cases, the manganese ion lies in the center of a distorted octahedron characterized by an elongation along the tetragonal axis. Their electronic properties were investigated by multifrequency EPR (190-475 GHz) performed in the solid state at different temperatures (5-15 K). This study confirms our previous results and further shows that: i) the sign of D is correlated with the nature of the tetragonal distortion; ii) the magnitude of D is not sensitive to the nature of the anions in our series of rhombic complexes, contrary to the porphyrinic systems; iii) the |E/D| values (0.124 for 1 and 0.085 for 2) are smaller compared to those found for the [Mn(L)(X)3] complexes (in the range of 0.146 to 0.234); and iv) the E term increases when the ligand-field strength of the equatorial ligands decreases.

AB - The isolation, structural characterization, and electronic properties of two six-coordinated chloromanganese (III) complexes, [Mn(terpy)(Cl)3] (1) and [Mn(Phterpy)(Cl)3] (2), are reported (terpy=2,2′: 6′2″-terpyridine, Phterpy=4′-phenyl-2,2′:6′, 2″-terpyridine). These complexes complement a series of mononuclear azide and fluoride Mn(III) complexes synthesized with neutral N-tridentate ligands, [Mn(L)(X)3] (X=F- or N3- and L=terpy or bpea [N,N-bis(2-pyridylmethyl)-ethylamine)], previously described. Similar to these previous complexes, 1 and 2 exhibit a Jahn-Teller distortion of the octahedron, characteristic of a high-spin Mn(III) complex (S=2). The analysis of the crystallographic data shows that, in both cases, the manganese ion lies in the center of a distorted octahedron characterized by an elongation along the tetragonal axis. Their electronic properties were investigated by multifrequency EPR (190-475 GHz) performed in the solid state at different temperatures (5-15 K). This study confirms our previous results and further shows that: i) the sign of D is correlated with the nature of the tetragonal distortion; ii) the magnitude of D is not sensitive to the nature of the anions in our series of rhombic complexes, contrary to the porphyrinic systems; iii) the |E/D| values (0.124 for 1 and 0.085 for 2) are smaller compared to those found for the [Mn(L)(X)3] complexes (in the range of 0.146 to 0.234); and iv) the E term increases when the ligand-field strength of the equatorial ligands decreases.

KW - Electronic properties

KW - EPR spectroscopy

KW - Manganese

KW - Multifrequency EPR spectroscopy

KW - N ligands

UR - http://www.scopus.com/inward/record.url?scp=16644392752&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=16644392752&partnerID=8YFLogxK

U2 - 10.1002/cphc.200400484

DO - 10.1002/cphc.200400484

M3 - Article

C2 - 15799481

AN - SCOPUS:16644392752

VL - 6

SP - 541

EP - 546

JO - ChemPhysChem

JF - ChemPhysChem

SN - 1439-4235

IS - 3

ER -