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Title: Neutral catecholate derivatives of manganese and iron: Synthesis and characterization of the metal-oxygen cubane-like species M sub 4 (DBCat) sub 4 (py) sub 6 (M = Mn, Fe), the trinuclear complex Mn sub 3 (DBCat) sub 4 (py) sub 4 , and the dimers M sub 2 (DBCat) sub 2 (py) sub n (M = Mn, n = 6; M = Fe, n = 4, 6)

Abstract

The synthesis and characterization of several new catecholate derivatives of manganese and iron are described. The reaction of 3,5-di-tert-butylcatechol (DBCatH{sub 2}) with the amides M(N(SiMe{sub 3}){sub 2}){sub 2} (M = Mn, Fe) in the presence of pyridine (py) affords the title compounds in high yield. The dimers Mn{sub 2}(DBCat){sub 2}(py){sub 6} (1) and Fe{sub 2}(DBCat){sub 2}(py){sub n} (n = 4 (4a), 6 (4b)) are obtained by treatment of catechol with the appropriate amide in pyridine. In hexane or toluene, this reaction gives the tetrametallic species M{sub 4}(DBCat){sub 4}(py){sub 6} (M = Mn (2), Fe (5)) upon the addition of 2 equiv of pyridine or, in the case of 2, by recrystallization of the dimer from toluene. Mn{sub 3}(DBCat){sub 4}(py){sub 4} (3) is obtained by slow air oxidation of 2 or by addition of 1/3 equiv of 3,5-di-tert-butyl-o-benzoquinone to the reaction of Mn(N(SiMe{sub 3}){sub 2}){sub 2} with DBCatH{sub 2} in hexane with subsequent addition of pyridine. Compounds 1-5 were characterized by infrared, UV-visible, {sup 1}H NMR, and EPR spectroscopy and X-ray crystallography.

Authors:
;  [1]
  1. Univ. of California, Davis (United States)
Publication Date:
OSTI Identifier:
6967328
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry; (United States)
Additional Journal Information:
Journal Volume: 31:6; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; IRON COMPLEXES; CHEMICAL PREPARATION; MANGANESE COMPLEXES; AMIDES; BOND ANGLE; BOND LENGTHS; CHEMICAL REACTION KINETICS; CRYSTAL STRUCTURE; DERIVATIZATION; DIMERS; ELECTRON SPIN RESONANCE; ELECTRON TRANSFER; INFRARED SPECTRA; LIGANDS; NMR SPECTRA; OXIDATION; PHOTOCHEMICAL REACTIONS; PYRIDINES; PYROCATECHOL; RECRYSTALLIZATION; TRIGONAL LATTICES; ULTRAVIOLET SPECTRA; X-RAY DIFFRACTION; AROMATICS; AZINES; CHEMICAL REACTIONS; COHERENT SCATTERING; COMPLEXES; CRYSTAL LATTICES; DEVELOPERS; DIFFRACTION; DIMENSIONS; HETEROCYCLIC COMPOUNDS; HYDROXY COMPOUNDS; KINETICS; LENGTH; MAGNETIC RESONANCE; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; PHENOLS; POLYPHENOLS; REACTION KINETICS; RESONANCE; SCATTERING; SPECTRA; SYNTHESIS; TRANSITION ELEMENT COMPLEXES; 140505* - Solar Energy Conversion- Photochemical, Photobiological, & Thermochemical Conversion- (1980-); 400500 - Photochemistry

Citation Formats

Shoner, S C, and Power, P P. Neutral catecholate derivatives of manganese and iron: Synthesis and characterization of the metal-oxygen cubane-like species M sub 4 (DBCat) sub 4 (py) sub 6 (M = Mn, Fe), the trinuclear complex Mn sub 3 (DBCat) sub 4 (py) sub 4 , and the dimers M sub 2 (DBCat) sub 2 (py) sub n (M = Mn, n = 6; M = Fe, n = 4, 6). United States: N. p., 1992. Web. doi:10.1021/ic00032a016.
Shoner, S C, & Power, P P. Neutral catecholate derivatives of manganese and iron: Synthesis and characterization of the metal-oxygen cubane-like species M sub 4 (DBCat) sub 4 (py) sub 6 (M = Mn, Fe), the trinuclear complex Mn sub 3 (DBCat) sub 4 (py) sub 4 , and the dimers M sub 2 (DBCat) sub 2 (py) sub n (M = Mn, n = 6; M = Fe, n = 4, 6). United States. doi:10.1021/ic00032a016.
Shoner, S C, and Power, P P. Wed . "Neutral catecholate derivatives of manganese and iron: Synthesis and characterization of the metal-oxygen cubane-like species M sub 4 (DBCat) sub 4 (py) sub 6 (M = Mn, Fe), the trinuclear complex Mn sub 3 (DBCat) sub 4 (py) sub 4 , and the dimers M sub 2 (DBCat) sub 2 (py) sub n (M = Mn, n = 6; M = Fe, n = 4, 6)". United States. doi:10.1021/ic00032a016.
@article{osti_6967328,
title = {Neutral catecholate derivatives of manganese and iron: Synthesis and characterization of the metal-oxygen cubane-like species M sub 4 (DBCat) sub 4 (py) sub 6 (M = Mn, Fe), the trinuclear complex Mn sub 3 (DBCat) sub 4 (py) sub 4 , and the dimers M sub 2 (DBCat) sub 2 (py) sub n (M = Mn, n = 6; M = Fe, n = 4, 6)},
author = {Shoner, S C and Power, P P},
abstractNote = {The synthesis and characterization of several new catecholate derivatives of manganese and iron are described. The reaction of 3,5-di-tert-butylcatechol (DBCatH{sub 2}) with the amides M(N(SiMe{sub 3}){sub 2}){sub 2} (M = Mn, Fe) in the presence of pyridine (py) affords the title compounds in high yield. The dimers Mn{sub 2}(DBCat){sub 2}(py){sub 6} (1) and Fe{sub 2}(DBCat){sub 2}(py){sub n} (n = 4 (4a), 6 (4b)) are obtained by treatment of catechol with the appropriate amide in pyridine. In hexane or toluene, this reaction gives the tetrametallic species M{sub 4}(DBCat){sub 4}(py){sub 6} (M = Mn (2), Fe (5)) upon the addition of 2 equiv of pyridine or, in the case of 2, by recrystallization of the dimer from toluene. Mn{sub 3}(DBCat){sub 4}(py){sub 4} (3) is obtained by slow air oxidation of 2 or by addition of 1/3 equiv of 3,5-di-tert-butyl-o-benzoquinone to the reaction of Mn(N(SiMe{sub 3}){sub 2}){sub 2} with DBCatH{sub 2} in hexane with subsequent addition of pyridine. Compounds 1-5 were characterized by infrared, UV-visible, {sup 1}H NMR, and EPR spectroscopy and X-ray crystallography.},
doi = {10.1021/ic00032a016},
journal = {Inorganic Chemistry; (United States)},
issn = {0020-1669},
number = ,
volume = 31:6,
place = {United States},
year = {1992},
month = {3}
}