Metal thermochemistry

Laury, M.L. and Wilson, A.K. (2013) Performance of density functional theory for second row (4d) transition metal thermochemistry. /. Chem Theory Comput, 9, 3939—3946. 

A number of reviews have appeared covering the various aspects of borate glasses. The stmcture, physical properties, thermochemistry, reactions, phase equihbria, and electrical properties of alkah borate melts and glasses have been presented (73). The apphcation of x-ray diffraction, nmr, Raman scattering, in spectroscopy, and esr to stmctural analysis is available (26). Phase-equihbrium diagrams for a large number of anhydrous borate systems are included in a compilation (145), and thermochemical data on the anhydrous alkah metal borates have been compiled (17). 

G. Pilcher, Thermochemistry of Organo-metallic Compounds11, Academic Press, NY... 

Thermochemistry and oxidation potentials of the platinum group metals and their compounds. R. N. Goldberg and L. G. HepleT, Chem. Rev., 1968, 68,229-252 (212). 

Thermochemistry of gaseous transition metal complexes of group V and VI ligands. P. M. Burken-shaw and C. T. Mortimer, Coord. Chem. Rev., 1983,48,101-155 (110). 

Thermochemistry of metal-polyamine complexes. P. Paoletti, L. Fabrizzi and R. Barbucci, Inorg. Chim. Acta, Rev., 1973,7, 43-68 (100). 

Transition Metal Systems Bearing a Nucleophilic Carbene Ancillary Ligand from Thermochemistry... 

Armentrout, R B., Kickel, B. L., 1996, Gas-Phase Thermochemistry of Transition Metal Ligand Systems Reassessment of Values and Periodic Trends in Organometallic Ion Chemistry, Freiser, B. S. (ed.), Kluwer, Amsterdam. 

Blomberg, M. R. A., Siegbahn, P. E. M., 1998, Calculating Bond Strengths for Transition Metal Complexes in Computational Thermochemistry, Irikura, K. K., Frurip, D. J. (eds.), American Chemical Society Symposium Series 677, Washington, DC. 

Jafarpour, Laleh, and Nolan, Steven P., Transition-Metal Systems Bearing a Nucleophilic Carbene Ancillary Ligand from Thermochemistry to Catalysis.. 46 181... 

The application of newer methods to studies of gas phase organometallic reactions will lead to the development of routine techniques for determination of the thermochemistry of organometallic species. The examples discussed above demonstrate that an analysis of kinetic energy release distributions for exothermic reactions yields accurate metal ligand bond dissociation energies. This can be extended to include neutrals as well as ions. For example, reaction 15 has been used to determine accurate bond dissociation energies for Co-H and C0-CH3 (57). 

It is not intended to discuss the details of the various methods of thermochemical measurement and the evaluation of results. This has been done in authoritative articles by Skinner1 and by Pilcher2) which have appeared recently, and which deal specifically with the thermochemistry of organometallic compounds. Instead this article will survey the results which may be derived from the information which is available and relate them to features of metal carbonyl chemistry in particular. 

Pilcher, G. Thermochemistry of organometallic compounds containing metal-carbon linkages. MTP Review of Science. Series 2. Physical chemistry, Vol. 10. Chapter 2. 1975, p. 45 Cox, J. D., Pilcher, G. Thermochemistry of organic and organometallic compounds. London Academic Press 1970... 

G. Pilcher, H. A. Skinner. Thermochemistry of Organometallic Compounds. In The Chemistry of the Metal-Metal Bond F. R. Hartley, S. Patai, Eds. Wiley New York, 1982 chapter 2. 

Much of the discussion of oxygen flame calorimetry presented in section 7.3 is directly applicable to fluorine flame calorimetry. As in the case of bomb calorimetry, however, the special properties of fluorine combustion systems and problems associated with handling fluorine require a somewhat different experimental method [109,115,116]. Thus, for example, a metal burner should be used. Also, the fact that the mixing of many gases with F2 may lead to spontaneous ignition hinders the use of a premixed flame. Fluorine combustion calorimetry has been used to study the thermochemistry of important reactions, such as... 

The determination of the heat capacity of a substance as a function of the temperature is by itself a very important application of DSC, because it may lead to values of the thermodynamic functions S%, //-" — //q, and Gy, mentioned in chapter 2. An example is the study of C6o carried out by Wunderlich and co-workers [271], The application of DSC in the area of molecular thermochemistry has been particularly important to investigate trends in transition metal-ligand bond dissociation enthalpies. The typical approach used in these studies, and its limitations, can be illustrated through the analysis of the reaction 12.27, carried out by Mortimer and co-workers [272] ... 

J. J. Christensen. Metal-Ligand Heats and Related Thermodynamic Quantities by Titration Calorimetry. In Thermochemistry and Its Applications to Chemical and Biochemical Systems M. A. V. Ribeiro da Silva, Ed. NATO ASI Series C, Riedel Dordrecht, 1984 253-273. 

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