Models, for organometallics

Marks TJ, Yang W, Stern CL (1991) Models for organometallic molecule-support complexes. Very large counterion modulation of cationic actinide alkyl reactivity. Organometallics 10 840-842... 

The following is a comprehensive smwey of the chemistry of macrocycles comprised entirely of phenyl and acetylenic moieties. Although over fom" decades old, this area of research has come into its own just in the last few years. Widespread interest in the field has been spurred by recent discoveries utilizing these compoimds as ligands for organometallic chemistry, hosts for binding guest molecules, models of synthetic carbon allotropes, and precursors to fullerenes and other carbon-rich materials. This review will discuss the preparation of a tremendous variety of novel structm-es and detail the development of versatile synthetic methods for macro cycle construction. 

Bohm, L. L, Franke, R., Thum, G., The microreactors as a model for the description of the ethylene polymerization with heterogeneous catalysts, in Kaminsky, W., Sinn, H. (Eds.), Transition metals and organometallics as catalysts for olefln polymerization, pp. 391-403, Springer-Verlag, Berlin (1988). 

The articles by J. R. Anderson, J. H. Sinfelt, and R. B. Moyes and P. B. Wells, on the other hand, deal with a classical field, namely hydrocarbons on metals. The pattern of modem wTork here still very much reflects the important role in the academic studies of deuterium exchange reactions and the mechanisms advanced by pioneers like Horiuti and Polanyi, the Farkas brothers, Rideal, Tw igg, H. S. Taylor, and Turkevich. Using this method, Anderson takes ultrathin metal films with their separated crystallites as idealized models for supported metal catalysts. Sinfelt is concerned with hydrogcnolysis on supported metals and relates the activity to the percentage d character of the metallic bond. Moyes and Wells deal with the modes of chemisorption of benzene, drawing on the results of physical techniques and the ideas of the organometallic chemists in their discussions. 

The relationship between "conventional" and "high energy" processes in organometallic chemistry is defined. The growth of metal atom chemistry is surveyed as a model for the impact of a "high energy process" on the field of organometallic chemistry. 

Tripodal N V,0-Ligands for Metalloenzyme Models and Organometallics Nicolai Burzlaff... 

Acetylene and ethylene are two convenient models for quantitative studies. A large number of studies have been carried out on these systems but the purpose of this section is not to give a comprehensive discussion of these transformations. For these reasons, the numerical values given here are the one used later for the organometallic systems. B3PW91/6-3 l(d,p) calculations [8] give values in accord with this simple description (equations 3 and 4)... 

This mechanistic question is one of the examples of the success of density functional theory methods in organometallic chemistry. Earlier work on the reaction mechanism could not discriminate between the two alternatives. Analysis of the different orbitals based on extended Hiickel calculations came to the result that the [3+2] pathway is more likely, but could not exclude the possibility of a [2+2] pathway [13]. Similar conclusions where obtained from the results of Hartree-Fock calculations in combination with QCISD(T) single point calculations [21], Attempts to use Ru04 as a model for osmium tetraoxide indicated that the formation of an oxetane is less favorable compared to the [3+2] pathway, but still possible [22, 23],... 

Lyon, E. J., Georgakaki, I. R, Reibenspies, J. H. and Darensbourg, M. Y. (1999) Carbon monoxide and cyanide ligands in a classical organometallic complex model for Fe-only hydrogenase. Angew. Chem. Int. Ed. Engl., 38, 3178-80. 

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