Metal complexes, of molecular

METAL COMPLEXES OF MOLECULAR NITROGEN AND RELATED SPECIES... 

This volume follows the organizational patterns initiated in Volumes X and XI. Syntheses are grouped according to interest area, using this criterion, we have placed in Vol. XII a chapter on Metal Complexes of Molecular Nitrogen and one on Significant Solids. More traditional chapter headings such as Nonmetal Systems and Boron Compounds also fit appropriately under the criterion of interest areas. 

Aminoboranes have been used as ligands in complexes with transition metals (66) in one instance giving a rare example of two-coordinate, non-t/ transition-metal complexes. The molecular stmcture of the iron complex Fe[N(Mes)B(Mes)2]2 where Mes = is shown in Figure 1. The... 

Metal complexes of porphine and azaporphine compounds as catalysts of reactions involving oxidation of molecular oxygen. N. S. Enikolopyan, K. A. Bogdanova and K. A. Askarov, Russ. Chem. Rev. (Engl. Transl), 1983, 52,13-26 (161). 

Inclusion complexes of molecular transition metal hosts. T. J. Meade and D. H. Busch, Prog. Inorg. Chem., 1985,33, 59(331). 

In the field of porous supramolecular metal complexes, both molecular and extended-solid materials have been extensively studied in recent years. A particularly well-studied class of compounds is the metal-containing molecular squares, that is, square-shaped porous tetrameric structures (30,108). These have been prepared by several approaches, the most common being the reaction of an organic bridging ligand with a metal complex that has available cis-coordination sites (109-113) (Fig. 13). However, the resulting metal centers are usually coordinatively saturated, which makes it difficult for guest molecules to interact directly with the metal atoms. 

It is well-established that the molecular and electronic structures of metal complexes of azamacrocycles are greatly affected upon N-alkylation (197). This is mainly due to two factors (a) the decrease of the ligand field strength and (b) the increase in the steric requirements upon going from a secondary to a tertiary amine donor function (251). To examine whether the properties of the dinuclear amine-thiophenolate complexes are affected by the N-alkyl substituents, analogous complexes of the... 

A) Dative Hi coordination. Metals with empty orbitals can accept charge from the donor molecular hydrogen. Alternatively, this... 

Dative and synergistic complexation of dihydrogen Direct observation of complexation of molecular H2 at metal centers is a relatively recent phenomenon. Virtually all such complexes exhibit relatively minor elongation of the H—H bond, indicating that description of these species as molecular-H2 complexes (rather than, e.g., metal dihydrides or some intermediary resonance mixture) is well justified. Experimentally observed molecular H2 complexes of the synergistic type are common, but those of simple dative type are not. 

For an overview of complexation of molecular dihydrogen to metals, see G. J. Kubas, Metal Dihydrogen and Sigma-Bond Complexes Structure, Theory, and Reactivity (New York, Kluwer Academic, 2001). 

Despite the above aspects of the interaction of molecular oxygen with metal fragments, we will limit our electrochemical discussion to the reactivity of transition metal complexes with molecular oxygen in the context of modelling the dioxygen transport. 

Cassoux P, Valade L, Kobayashi H, Kobayashi A, Clark RA, Underhill AE (1991) Molecular metals and superconductors derived from metal complexes of l,3-dithiol-2-thione-4, 5-dithiolate (dmit). Coord Chem Rev 110 115-160... 

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