thermochimica
acta
ELSEVIER Thermochimica Acta 287 (1996) 111-129
M6ssbauer spectroscopic and thermal decomposition
studies of alkylamine and nitrogen heterocyclic
substituted pentacyanoferrate(II) complexes
R.B. Lanjewar t, S. Kawata a, T. Nawa a, S. Kitagawa a
A.N. Garg b M. Katada a,,
" Radioisotope Research centre, Tokyo Metropolitan University, Minami osawa, Hachioji. Tokyo 192-03
Japan
b Department of Chemistry, Nagpur University, Naypur. 440 010, India
Received 24 January 1996; accepted 19 March 1996
Abstract
Substituted pentacyanoferrate(II)complexes Na3[Fe(CN)sL]'xH20 have been obtained for
di-sec-butylamine, tri-n-amylamine, pyrazole, pyrazine, pyrrole, and 2-,3- and 4-cyanopyridine.
Microanalysis, UV-visible, infrared, and M6ssbauer spectroscopies, TGA DTG and XRD were
used to characterize the complexes, Each complex has an absorption band in the visible region
that is assigned to a d-d transition. M6ssbauer parameters are used to classify the various
ligands according to their a- and ~- bonding abilities. The M/Sssbauer spectra of these complexes
exhibit a quadrupole doublet, AE o = 0.71-0.84 mm s- 1 at room temperature. The isomer shift
(6) values fall within 0.00 + 0.02 mm s- l which suggests that the iron atom is in a + 2 low-spin
state. Thermolysis of the solids leads to water release, ligand release and/or decomposition,
yielding elemental metal, metal carbides, haematite and magnetite.
Keywords: Thermal decomposition; M6ssbauer spectroscopy; Pentacyanoferrates(II); Iron(I)
complex
1. Introduction
Substantial interest in substituted pentacyanoferrates(II) continues. A wide variety
of substituted pentacyanoferrates(II) have been synthesized and extensively studied by
* Corresponding author.
1 On leave from A.N. College, Anandwan 442 914, India.
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