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Thermal Deamination-anation in Cobalt(III) Thiocyanate Complexes. Novel decarbonylation of the equatorial amide ligand

Authors
  • Amirnasr, M.1
  • Houriet, R.2
  • Meghdadi, S.3
  • 1 Swiss Federal Institute of Technology, Institute of Physical Chemistry, Lausanne, CH-1015, Switzerland , Lausanne
  • 2 Swiss Federal Institute of Technology, Department of Materials Science, Lausanne, CH-1015, Switzerland , Lausanne
  • 3 Isfahan University of Technology, Department of Chemistry, Isfahan, 84154, Iran , Isfahan
Type
Published Article
Journal
Journal of Thermal Analysis and Calorimetry
Publisher
Springer-Verlag
Publication Date
Mar 01, 2002
Volume
67
Issue
3
Pages
523–533
Identifiers
DOI: 10.1023/A:1014380015981
Source
Springer Nature
Keywords
License
Yellow

Abstract

The solid state thermal behavior of trans-[Co(bpb)(amine)2]NCS⋅H2O complexes where (bpb)=[N,N’-bis(2-pyridinecarboxamido-N)-1,2-benzene], and amine=pyrrolidine (prldn)(1), and benzylamine (bzlan) (2), and trans-[Co(bpb)(piperidine)2]ClO4⋅H2O (3) (mixed with KSCN), has been studied using thermoanalytical techniques, infrared spectroscopy, and pyrolysis coupled to both infrared and mass spectrometry, PY/FTIR and PY/MS. The deamination-anation reaction is clearly observed for all three complexes. The estimated values of Ea for the deamination-anation are: Ea(1)=246.8 kJ mol−1, Ea(2)=255.7 kJ mol−1, Ea(3)=234.7 kJmol−1. The trend in Ea values is rationalized based on the ligand field strength of the amines and the structural effects. A novel decarbonylation of the amide CO group from the equatorial ligand is observed after the release of one amine molecule. This process has been monitored for complex (1) by FTIR in the carbonyl region and by mass spectrometry for the detection of CO2 at 280°C. The activation energy of this process is estimated for complex (1) (662.5 kJ mol−1). The reaction scheme for the observed reactions is proposed.

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