Synthesis, X-ray structure, electrochemical, and EPR studies of a pentacoordinated Mn(II) tetramethylcyclam complex

Citation
C. Bucher et al., Synthesis, X-ray structure, electrochemical, and EPR studies of a pentacoordinated Mn(II) tetramethylcyclam complex, INORG CHEM, 40(22), 2001, pp. 5722
Citations number
47
Categorie Soggetti
Inorganic & Nuclear Chemistry
Journal title
INORGANIC CHEMISTRY
ISSN journal
00201669 → ACNP
Volume
40
Issue
22
Year of publication
2001
Database
ISI
SICI code
0020-1669(20011022)40:22<5722:SXSEAE>2.0.ZU;2-8
Abstract
The synthesis and full characterization of [(tmc)MnCl].X (where tine is 1,4 ,8,11-tetramethyl-1,4,8,1 1-tetraazacyclotetradecane and X is BPh4- or BF4- ) are reported. The complex is of type I geometry. The manganese ion is pen tacoordinated by the four tertiary nitrogen atoms of the macrocycle and one axial chloride. Variable-temperature magnetic susceptibility da ta indicat e that the oxidation state of the manganese ion is +II with S = 5/2. The EP R spectrum exhibits unusual signals, with the main derivative line at g = 3 .7 and transitions at more than 900 mT. The cyclic voltammogram of this der ivative consists of two reversible systems at +1.14 and +1.36 V vs SCE rela ted by a chemical equilibrium attributed to an isomerization process.