Inorganic metalloporphyrin

A recent development concerns the use of polyanions of the type [XMi 039M (0H2)]". In this type, the M atom easily becomes coordinatively unsaturated by dehydration (255). The resulting dehydrated anion, [XMhOjqM ]", can be considered an inorganic metalloporphyrin analog (322, 364, 365). Oxidation catalysis by these polyanions is described in Sections VIII and IX. Here, the catalytic performance and stability are compared with that of metalloporphyrin. 

Figure 1. Representative polyoxometalates in polyhedral notation. A. the isopolyanion decatungstate (Wio032 ) (C>4h point group symmetry) and B. the heteropolyanion family, (TM)PWii039 , where TM is a first row divalent transition metal ion, P is the heteroatom (Cs point group symmetry). In the latter class of complexes, which constitute functional oxidatively resistant inorganic metalloporphyrin analogs, P is one of many elements that can function as the heteroatom. The darker octahedron on the surface and the veiy dark internal tetrahedron of B represent the TM ion and the heteroatom, respectively. In polyhedral notation a complementary notation to ball-and-stick or bond representations, the vertices of the polyhedra, principally W06 octahedra, are the nuclei of the oxygen atoms. The metal atoms lie inside each polyhedron.

Unlike metalloporphyrins, the nonporphyrinic metal compounds are poorly characterized with respect to molecular structure and properties. Examining the nature of the nickel and vanadium in these compounds is important from the standpoint that often most of the Ni and V in a petroleum is nonporphyrinic, as shown in Table II. Sugihara et al. (1970) suggested that the nonporphyrin metal compounds comprise a wide variety of coordinated complexes resulting from the reaction of inorganic forms of the metals with polar organic molecules. Larson and Beuther (1966) speculated that the nonporphyrinic metal complexes are simply... 

A thorough electrochemical characterization of new metalloporphyrins is nowadays state of the art for the synthetic inorganic chemist. In many of the papers cited in Sects. 3 and 4, a characterization of the new complexes by cyclic voltametry and electrolysis at controlled potential has been done. Thin-layer spectroelectrochemistry is very fruitful [346]. Fortunately, apart from classical articles of Davis et al. [347], Felton et al. [292], Fuhrhop et al. [293], Buchler et al. [190], more recent reviews of Kadish et al. are available which systematically cover the field of general metalloporphyrins [294] or organometallic porphyrin complexes [306]. Therefore, a short, update of these articles will be given in the form of Table 7. For details, the reader is referred to the original literature. 

Applications are varied, from catalysis of organic and inorganic reactions to electron transfer to and from molecules of biological interest. For example, it has been shown that ruthenium(IV) immobilized inside PVP catalyses organic oxidations such as that of propan-2-ol to acetone19. The electroreduction of oxygen (important in fuel cells, Section 15.10) is catalysed by metalloporphyrins and metallophthalocyanines20. The... 

With almost all of the conceivable coordination chemistry of the expanded porphyrins still left to be explored, it cannot be over-stres that the potential for new chemistry is enormous. This is i rticularly true when account is made of the fact that the chemistry of the metalloporphyrins has played a dominant role in modern inorganic chemistry. What with the possibility to enhance the stability of imusual coordination geometries (and, perhaps oxidations states) and the ability to form stable coordination complexes with a variety of unusual cations including those of the lanthanide and actinide series, the potential for new inorganic and organometallic discoveries are almost unlimited. For instance, as with the porphyrins, one may envision linear arrays of stacked expanded porphyrin macrocycles which may have unique conducting properties and/or which could display beneficial super- or semiconducting capabilities. Here, of course, the ability to coordinate not only to cations but also to anions could prove to be of tremendous utility. 

In terms of availability, number, and nature of surface groups, surface area, pore size, pore volume, and form and size of the particles, silica has been undoubtedly the most preferred inorganic support. Suitable modification is possible via the surface silanol groups, which can react either directly with an appropriate metal complex or with an intermediate ligand group. Direct surface bonding has often been practiced, e. g., for the anchoring of metal carbonyl complexes [14] (eq. (11)), carbonyl clusters [26], polymerization catalysts [21, 62], or other special systems, e. g., 7r-allyl complexes [63] or metalloporphyrins [64]. 

C. L. Hill, R. B. Brown Jr., Sustained epoxidation of olefins by oxygen donors catalyzed by transition metal-substituted polyoxometalates, oxidatively resistant inorganic analogs of metalloporphyrins, J. Am. Chem. Soc. 108 (1986) 536. 

G.V. Buxton, Pulse Radiolysis Studies on Metalloproteins and Metalloporphyrins, in Advances in Inorganic and Bioinorganic Mechanisms, A.G. Sykes, ed.. Academic Press, Orlando, FL, 1984, Vol. 3, p. 131. 

---