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Thermal degradation of the transition metal carbonyl complexes

I. TG and DSC of monodentate bis-(diphenylphosphino)-methane substituted carbonyl complexes of chromium, molybdenum and tungsten

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Abstract

The thermal degradation of three monosubstituted hexacarbonyl complexes, M(CO)5(dppm) (whereM=Cr, Mo and W;dppm=Bis-(diphenylphosphino)-methane) has been studied using TG and DSC technics and their results reported. All the complexes facilely lose a carbonyl ligand (CO) below 200 °C. The kinetic analysis on the molybdenum complex suggested a first order dissociation pathway for this decarbonylation process. Dephosphination occurred at high temperature, followed by further decarbonylations. The enthalpy changes associated with the first decarbonylation are reported. The measured kinetic parameters are in good agreement with the literature values on similar systems obtained from solution studies.

Zusammenfassung

Der thermische Abbau von drei monosubstituierten Hexacarbonyl-Komplexen des Typs M(CO)5(dppm) (M=Cr, Mo oder W; dppm=Bis-(diphenylphosphino)-methan) wurden mittels TG und DSC untersucht. Alle diese Komplexe geben unterhalb 200 °C leicht einen Carbonylliganden (CO) ab. Die für den Molybdänkomplex ausgeführte kinetische Analyse deutet auf einen Dissoziationsverlauf erster Ordnung für diesen Decarbonylierungsprozeß hin. Bei hohen Temperaturen erfolgt Dephosphinierung, gefolgt von weiterer Decarbonylierung. Die sich auf den ersten Decarbonylierungsschritt beziehenden Enthalpieänderungen werden angegeben. Die gemessenen kinetischen Parameter stimmen gut mit Literaturwerten ähnlicher Systeme überein.

Резюме

Методом ТГ и ДСК изуче но термическое разложение трех моно замещенных гексакарбонильных к омплексов M(CO)5(dppm), гдеM=Cr, Мо и W;dppm=бисдифенилфосфино-метан. При температуре ниже 200° комплексы легко тер яют карбонильный лиганд. Кинетический анализ реакции разло жения молибденового компл екса указывает на первый порядок реакц ии декарбонилирован ия. Потеря фосфорорганическог о лиганда протекает при более высокой тем пературе, за которой с ледует дальнейшее декарбон илирование. Приведено изменение энтальпии, связанное с первичной реакцией декарбонил ирования. Полученные кинетиче ские параметры хорош о согласуются с литера турными значениями, найденными для подоб ных систем в растворе.

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Authors and Affiliations

  1. Department of Chemistry, National University of Singapore, 0511, Kent Ridge, Singapore

    H. S. O. Chan, T. S. A. Hor, C. S. M. Chiam & T. C. Chong

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  1. H. S. O. Chan
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  2. T. S. A. Hor
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  3. C. S. M. Chiam
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  4. T. C. Chong
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Chan, H.S.O., Hor, T.S.A., Chiam, C.S.M. et al. Thermal degradation of the transition metal carbonyl complexes. Journal of Thermal Analysis 32, 1115–1126 (1987). https://doi.org/10.1007/BF01905166

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  • DOI: https://doi.org/10.1007/BF01905166

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