Thermally induced isomerization and decomposition of N-methyl-1,3-propanediamine complexes of nickel (II) in the solid state

Ghosh, Ashutosh ; Koner, Subratanath ; Chaudhuri, Nirmalendu Ray (1988) Thermally induced isomerization and decomposition of N-methyl-1,3-propanediamine complexes of nickel (II) in the solid state Thermochimica Acta, 124 . pp. 297-310. ISSN 0040-6031

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Official URL: http://www.sciencedirect.com/science/article/pii/0...

Related URL: http://dx.doi.org/10.1016/0040-6031(88)87032-1

Abstract

[NiL2(H2O)Cl]Cl•nH2O (L = N-methyl-1,3-propanediamine: n = 0 and 1). [NiL2X2] [X = Br, CF3CO2 and CCl3CO2] and [NiL2,(H2O)Y]•H2O (Y = SO2 and SeO4) have been synthesized and their thermal investigations have been carried out in the solid state. [NiL2(H2O)Cl]Cl•nH2O and [NiL2(H2O)Y]•H2O exist in the trans form. On deaquation they transform to cis-[NiL2Cl2] and cis-[NiL2Y]. [NiL2(SO2)] undergoes a reversible endothermic phase transition (117–169 °C ΔH = 6.5 kJ mol−1). The complex trans-[NiL2(CF3 CO2)2] has been found to transform into its isomer upon heating, showing an endotherm (135–150 °C, ΔH = 18.9 kJ mol−1); on keeping the product in a humid atmosphere (relative humidity 60–70 %), it reverts to its original form. [NiL2Cl2], [NiLCl2] and [NiL(SO4)] have been synthesized pyrolytically in the solid state from their parent diamine complexes. All the complexes possess octahedral geometry and diamine is chelated in all of them except in [NiL(SO4)] where it is bridged. The occurrence of phase transition phenomena is supposed to be due to conformational changes in the six-membered chelate rings.

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