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Synthesis, Characterization, Thermal Decomposition, and Kinetic Studies of Binuclear Sulfur‐Coordinated Tungsten(V) Complexes with Piperidine‐1‐carbodithioate
Author(s) -
Lozano Rafael,
de Jesús Fernando,
Cano de Santayana Mercedes,
Lozano M. Carmen
Publication year - 2008
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.200890170
Subject(s) - chemistry , piperidine , pyridine , arrhenius equation , thermal decomposition , thermogravimetric analysis , endothermic process , activation energy , medicinal chemistry , organic chemistry , adsorption
We describe the synthesis, characterization by IR and electronic spectra, magnetic susceptibility measurements, analytical data, kinetic study by differential‐scanning calorimetry, and thermogravimetric analysis of the thermal decomposition under N 2 of the adducts 2 – 7 with pyridine or substituted pyridines of bis(piperidine‐1‐carbodithioato‐ κS , κS ′)di‐ μ ‐thioxodithioxoditungsten(V) ( 1 ), to which the general formula [W 2 B 2 (pipCS 2 ) 2 S 2 ( μ ‐S) 2 ] is assigned (pipCS 2 =piperidine‐1‐carbodithioato and B=pyridine (py), 3‐methylpyridine (3‐Mepy), 4‐methylpyridine (4‐Mepy), 3,5‐dimethylpyridine (3,5‐Me 2 py), pyridin‐3‐amine (3‐pyNH 2 ), and pyridin‐4‐amine (4‐pyNH 2 )). For the endothermic process of loss of the coordinated base B, we calculated activation energies with a method reported previously by us; the mechanism and pre‐exponential Arrhenius factor of this reaction were also determined. A relationship between the pyridines' basicity, IR and electronic spectral data, and activation energies was established.