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Titolo:
CHARACTERIZATION OF THE STRUCTURAL AND ELECTRONIC-PROPERTIES OF SPIN-COUPLED DINUCLEAR COPPER(II) CENTERS BY PROTON NMR-SPECTROSCOPY
Autore:
BRINK JM; ROSE RA; HOLZ RC;
Indirizzi:
UTAH STATE UNIV,DEPT CHEM & BIOCHEM LOGAN UT 84322 UTAH STATE UNIV,DEPT CHEM & BIOCHEM LOGAN UT 84322
Titolo Testata:
Inorganic chemistry
fascicolo: 10, volume: 35, anno: 1996,
pagine: 2878 - 2885
SICI:
0020-1669(1996)35:10<2878:COTSAE>2.0.ZU;2-X
Fonte:
ISI
Lingua:
ENG
Soggetto:
MOLECULAR-STRUCTURE; MAGNETIC-PROPERTIES; HEMOCYANIN MODELS; COMPLEXES; BINUCLEAR; PROTEINS; LIGAND; IS)BIS(2-PYRIDYLMETHYL)AMINOMETHYL>-4-METHYLPHENOL; SYSTEM;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Science Citation Index Expanded
Citazioni:
39
Recensione:
Indirizzi per estratti:
Citazione:
J.M. Brink et al., "CHARACTERIZATION OF THE STRUCTURAL AND ELECTRONIC-PROPERTIES OF SPIN-COUPLED DINUCLEAR COPPER(II) CENTERS BY PROTON NMR-SPECTROSCOPY", Inorganic chemistry, 35(10), 1996, pp. 2878-2885

Abstract

The H-1 NMR spectra of a series of well-characterized mu-phenoxo and mu-alkoxo spin-coupled dicopper(II) complexes have been investigated. The complexes studied were [Cu-2(BPMP)(OH)](2+) (1) (BPMP = bis(2-pyridylmethyl)amino]methyl]-4-methylphenol), [Cu-2(CH(3)HXTA)(OH)](2-) (2)(CH(3)HXTA = 5-methyl-1,3-xylylene)bis(N-carboxymethylglycine), [Cu-2(m-XYL)(OH)](2+) (3) (m-XYL = 2,6-bis[[bis(2-pyridylethyl)amino]methyl]phenol), and [Cu-2(TBHP)(OAc)](2+) (4) (TBHP = zimidazolyl)methyl]-2-hydroxy-1,3-diaminopropane). The magnetic interactions of these complexes range from strongly antiferromagnetically to weakly ferromagnetically coupled. Both one- and two-dimensional (COSY) H-1 NMR methods wereused to facilitate the assignment of the hyperfine shifted H-1 NMR signals of each complex. COSY experiments provide clear cross signals for resonances < 200 Hz wide. These data have facilitated the assignmentof the hyperfine shifted H-1 NMR signals and have verified that the solid state structures exist in solution for each system studied. Assuming a paramagnetic dipolar relaxation mechanism, the crystallographically determined Cu-H distance (r) is proportional to T-1(1/6). All calculated Cu-H distances for 1-4 are within ca. 20% of the Cu-H distancesderived from X-ray crystallography. These data indicate that a paramagnetic dipolar relaxation mechanism is the dominant proton relaxation pathway for spin-coupled dicopper(II) centers. Our results indicate that H-1 NMR spectroscopy is an excellent tool with which to probe the solution structures of spin-coupled dicopper(II) centers in model complexes as well as biological systems.

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Documento generato il 01/12/20 alle ore 18:24:07