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Thermoanalytical study of linkage isomerism in coordination compounds

Part II: Solid state stepwise thermal interconversion of dinitro and dinitrito linkage isomers of trans-bis(ethylenediamine)cobalt(III) hexafluorophosphate

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Abstract

The non-isothermal differential scanning calorimetry (DSC) experiments revealed that linkage isomerization of both pure trans-[Co(en)2(ONO)2]PF6 (dinitrito isomer) and trans-[Co(en)2(NO2)2]PF6 (dinitro isomer) occurs in the solid state at elevated temperatures. The process was found to be exothermic for the dinitrito isomer and endothermic for dinitro isomer. The pure isomers could be considered to be in metastable states at ambient temperatures which would be converted to an equilibrium mixture of both isomers (stable state) upon heating. Since the isomerization of both isomers may be described as a two stages process, the corresponding DSC peaks have been resolved into two peaks by means of nonlinear curve fitting tools of PeakFit® software. The resolution of the peaks helped us to determine enthalpy changes of stepwise isomerization of both isomers. A first-order initial rate and Kissinger methods have been employed to estimate kinetic parameters of the stepwise isomerization reactions. The Kissinger method provided more reliable kinetic results. The high activation energy and positive entropy changes of isomerization of both isomers are considered as indication of a dissociative mechanism in solid state.

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References

  1. Szeman N, Walker MB, Farmer PJ. Photo- and thermal-induced linkage isomerizations in a peroxydithiocarbamate–Ru complex. Inorg Chim Acta. 2009;362:4013–6.

    Article  Google Scholar 

  2. Girma KB, Lorenz V, Blaurock S, Edelmann FT. Coordination chemistry of acrylamide. Coord Chem Rev. 2005;249:1283–93.

    Article  CAS  Google Scholar 

  3. Ohtsu H, Oka N, Yamaguchi T. Syntheses and properties of a series of oxo-centered triruthenium complexes with thiocyanate and nitrite as terminal ligand. Inorg Chim Acta. 2012;383:1–6.

    Article  CAS  Google Scholar 

  4. Goodwin J, Kurtikyan T, Standard J, Walsh R, Zheng B. Variation of oxo-transfer reactivity of (nitro)cobalt picket fence porphyrin with oxygen-donating ligands. Inorg Chem. 2005;44:2215–23.

    Article  CAS  Google Scholar 

  5. Ooms KJ, Wasylishen RE. NMR spectroscopy of the solid-state isomerization of nitrito- and nitro-pentamminecobalt(III) chloride. Can J Chem. 2006;84:300–8.

    Article  CAS  Google Scholar 

  6. Philips WM, Choi S, Larrabee JA. Kinetics of pentaamminenitritocobalt(III) to pentaamminenitrocobalt(III) linkage isomerization, revisited. J Chem Educ. 1990;67:267–9.

    Article  Google Scholar 

  7. Supriya S, Das SK. Reversible nitro–nitrito inter-conversion in a simple mono-nuclear nickel(II) complex [NiII{C6H4(NH2)2}2(NO2)2] in the solid state. Inorg Chem Commun. 2009;12:364–7.

    Article  Google Scholar 

  8. Novozhilova IV, Coppens P, Lee J. Experimental and density functional theoretical investigations of linkage isomerism in six-coordinate {FeNO} iron porphyrins with axia nitrosyl and nitro ligands. J Am Chem Soc. 2006;128:2093–104.

    Article  CAS  Google Scholar 

  9. Jackson WG, Lawrence GA, Oxygen-17 N.M.R. study of linkage isomerization in nitritopentaamminecobalt(III): evidence for intramolecular oxygen exchange. J Chem Soc Chem Commun. 1982;70–72.

  10. Jackson WG. Base-catalyzed linkage isomerization: an undergraduate inorganic kinetics experiment. J Chem Educ. 1981;58:734–8.

    Article  CAS  Google Scholar 

  11. Rindermann W, Eldik RV. Base-catalyzed isomerization reactions on nitro- and nitritobis(ethylenediamine)cobalt(III) complexes in aqueous solution. Inorg Chim Acta. 1983;68:35–9.

    Article  CAS  Google Scholar 

  12. Warren MR, Brayshaw SK, Johnson AL, Raithby PR, Schiffers S. Reversible 100% linkage isomerization in a single-crystal to single-crystal transformation: photocrystallographic identification of the metastable [Ni(dppe)(η1-ONO)Cl] isomer. Angew Chem Int Ed. 2009;48:5711–4.

    Article  CAS  Google Scholar 

  13. Virovets AV, Podberezskaya NV, Gromilov SA. Comparison of crystal structures in the series [M(NH3)5NO2]XY and [M(NH3)5ONO]XY, crystal structure of [Co(NH3)5NO2]I2. J Struct Chem. 1993;33:890–8.

    Article  Google Scholar 

  14. Boldyreva EV. Crystal-structure aspects of solid-state inner-sphere isomerization in nitro(nitrito)pentaamminecobalt(III) complexes. Russ J Coord Chem. 2001;27:297–323.

    Article  CAS  Google Scholar 

  15. Laskar IR, Das D, Mostafa GT, Lu H. First report on thermally induced nitro nitrito (O,O) linkage isomerization in diamine complexes of nickel(II) in the solid state: X-ray single crystal structural analyses of nitro and nitrito isomers. New J Chem. 2001;25:764–8.

    Article  Google Scholar 

  16. Eslami A. Thermoanalytical study of linkage isomerism in coordination compounds part I. Reinvestigation of thermodynamic and themokinetic of solid state interconversion of nitrito (ONO) and nitro (NO2) isomers of pentaamminecobalt(III) choride by means of DSC. Thermochim Acta. 2004;409:189–93.

    Article  CAS  Google Scholar 

  17. Lee J, Kovalevsky AY, Novozhilova IV, Bagley KA, Coppens P, Richer-Addo GB. Single- and double-linkage isomerism in a six-coordinated iron porphyrin containing nitrosyl and nitro ligands. J Am Chem Soc. 2004;126:7180–1.

    Article  CAS  Google Scholar 

  18. Rindermann W, Eldik RV, Kelm H. Mechanistic information from the effect of pressure on the linkage isomerization reactions of cis and trans-dinitritobis(ethylenediammine)cobalt(III) in aqueous acidic solution. Inorg Chim Acta. 1982;61:173–80.

    Article  CAS  Google Scholar 

  19. Seel VF, Meyer D. Kinetik der isomerisierung und der umsetzung von cis- und trans-dinitrito-di(aethylendiamin)-kobalt(III)-perchloraten mit stickstoffwasserstoffsaeure. Z Anorg Allg Chem. 1974;408:283–92.

    Article  CAS  Google Scholar 

  20. Fee WW, Garner CS, Harrowfield JNM. Identification of new chromium(III) nitrito complexes by means of the electronic spectrum of the nitrito ligand in dipolar aprotic solvents. Inorg Chem. 1967;6:87–93.

    Article  CAS  Google Scholar 

  21. Holtzclaw HF, Sheets DP, McCarty BD. Cis- and trans-dinitrobis(ethylenediamine)cobalt(III) nitrate. In: Bailar Jr JC, editor. Inorganic synthesis. New York: McGraw-Hill; 1953. p. 176–9.

    Chapter  Google Scholar 

  22. Seel VF, Meyer D. Darstellung und absorptions-spektren der dinitrito-di(aethylendiamin)-kobalt(III)-perchlorate. Z Anorg Allg Chem. 1974;408:275–82.

    Article  CAS  Google Scholar 

  23. Lantzke IR, Watts DW. Octahedral cobalt complexes in dipolar aprotic solvents. Aust J Chem. 1967;20:35–52.

    Article  CAS  Google Scholar 

  24. Nakamoto K. Infrared and Raman spectra of inorganic and coordination compounds. 4th ed. New York: Wiley; 1986.

    Google Scholar 

  25. De G, Biswas PK, Chaudhuri NR. Conformational changes of nickel(II) diamine complexes in the solid state. J Chem Soc Dalton Trans. 1984;2591–2598.

  26. Mukherjee AK, Koner S, Ghosh A, Chaudhuri NR, Mukherjee M, Welch AJ. Isomerism in bis(diethylenetriamine)nickel(II) thiocyanate: synthesis, solid-state interconversion and X-ray crystallographic study of sym-fac and mer isomers. J Chem Soc Dalton Trans. 1994;2367–2371.

  27. Boldyreva EV. Intramolecular linkage isomerization in the crystals of some Co(III)—ammine complexes—a link between inorganic and organic solid state chemistry. Mol Cryst Liq Cryst. 1994;242:17–52.

    Article  Google Scholar 

  28. Grenthe I, Nordin E. Nitrito-nitro linkage isomerization in the solid sate. 1. X-ray crystallographic studies of trans-bis(ethylenediammine)(isothiocyanato)nitrito- and trans-bis(ethylenediammine)(isothiocyanato)nitrocobalt(III) perchlorate and iodide. Inorg Chem. 1979;18:1109–16.

    Article  CAS  Google Scholar 

  29. Masciocchi N, Kolyshev A, Boldyreva E, Sironi A. Study of the linkage isomerization [Co(NH3)5NO2]Br2 ↔ [Co(NH3)5ONO]Br2 in the solid state by X-ray powder diffraction. Inorg Chem. 1994;33:2579–85.

    Article  CAS  Google Scholar 

  30. Grenthe I, Nordin E. Linkage isomerization in the solid sate. II. A comparison study of the structures of nitrito- and nitropentaamminecobalt(III) dichloride. Inorg Chem. 1869;18:1869–74.

    Article  Google Scholar 

  31. Vyazovkin S, Wight CA. Model-free and model-fitting approaches to kinetic analysis of isothermal and nonisothermal data. Thermochim Acta. 1999;340–341:53–68.

    Article  Google Scholar 

  32. Vyazovkina S, Burnhamb AK, Criadoc JM, Pérez-Maquedac LA, Popescud C, Sbirrazzuolie N. ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data. Thermochim Acta. 2011;520:1–19.

    Article  Google Scholar 

  33. Bigda R, Mianowski A. Influence of heating rate on kinetic quantities of solid phase thermal decomposition. J Therm Anal Calorim. 2006;84:453–65.

    Article  CAS  Google Scholar 

  34. Lin CP, Chang YM, Tseng JM. Comparisons of nth-order kinetic algorithms and kinetic model simulation on HMX by DSC tests. J Therm Anal Calorim. 2010;100:607–14.

    Article  CAS  Google Scholar 

  35. Ciofini H, Adamo C. Intrinsic and environmental effects on the kinetic and thermodynamics of linkage isomerization in nitritopentaamminecobalt(III) complexes. J Phys Chem A. 2001;105:1086–92.

    Article  CAS  Google Scholar 

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  1. Faculty of Chemistry, University of Mazandaran, P.O. Box 47416-95447, Babolsar, Iran

    Abbas Eslami & Nahid Hasani

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  1. Abbas Eslami
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  2. Nahid Hasani
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Correspondence to Abbas Eslami.

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Eslami, A., Hasani, N. Thermoanalytical study of linkage isomerism in coordination compounds . J Therm Anal Calorim 111, 193–201 (2013). https://doi.org/10.1007/s10973-012-2470-8

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