Coordination chemistry porphyrins

Self-Sorting Systems Based on Porphyrin Coordination Chemistry... 

The equilibrium constants K and f)2 increase as the ligand pKt increases. The increases in porphyrin basicity and solvent polarity also increase / 2, indicating the importance of the charge neutralization factor in the iron(III) porphyrin coordination chemistry (Table 6).86 For preparative purposes, five-coordinate complexes of the weak ligands are conveniently used to avoid contamination of the mixed ligand species Fe(Por)XL. 

Phosphorus(V) in its most stable oxidation state forms robust chelate complexes with the porphyrin, and retains the capability of binding two oxygen ligands in a frans-axial mode as outlined in Sect. 3. This strategy was used by Maiya [81,102-104] and Tanaka and Segawa [105]. The coordination chemistry of phosphorous(V) porphyrins is similar to germa-nium(IV), tin(IV), gallium(III), and aluminium(III) porphyrin coordination chemistry [102,106]. These metalloporphyrins were shown to form multiporphyrin complexes with phenol-substituted porphyrins. Because of the... 

Structural aspects and coordination chemistry of metal porphyrin complexes with emphasis on axial ligand binding to carbon donors and mono- and di-atomic nitrogen and oxygen donors. P. D. Smith, B. R. James and D. H. Dolphin, Coord. Chem. Rev., 1981,39, 31-75 (170). 

Coordination chemistry of manganese and porphyrins. M. Calvin, Rev. Pure Appl. Chem., 1965,15, 1-10 (9). 

Buchler JW, Dreher C, Kiinzel FM (1995) Synthesis and Coordination Chemistry of Noble Metal Porphyrins. 84 1-70... 

One step of the mechanism determined for the reaction of Rh(OEP)H with CO to give the formyl complex Rh(OEP)CHO involved the coordination of CO to the chain-carrying Rh(ll) porphyrin Rh(OEP)-, although there had been no direct evidence observed for this species.Since that time. Wayland has systematically developed the chemistry of Rh( 11) porphyrins coordinated to CO, and the chemistry is now well understood. 

A handbook on inorganic and coordination chemistry of porphyrins has been published.1765 Factor F430 is the nickel-hydrocorphinoid group of the enzyme methyl coenzyme M reductase.47,48 The mystery of this particular metalloprotein is one of the major reasons for the development of Ni11-porhyrin coordination chemistry, although not the only one. 

Metalloporphyrin reactivity and catalytic properties can also be controlled by modifications of the porphyrin core. Ni coordination chemistry of core-modified porphyrins has been reviewed.1791,1792 Several X-ray structures of four-, five-, and six-coordinate Ni11 complexes with oxa-, thia-, and dioxatetraarylporphyrins are known. 

Mashiko, T. Dolphin, D. Porphyrins, hydroporphyrins, azaporphyrins, phthalocyanines, corroles, corrins and related macrocycles. In Comprehensive Coordination Chemistry Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds. Pergamon Oxford, 1987, Vol. 2, Chapter 21.1. 

Buchler, J. W. Static coordination chemistry of metalloporphyrins. In Porphyrins and Metalloporphyrins, Smith, K. M., Ed. Elsevier Amsterdam, 1975, pp 157-231. 

Organometallic compounds play an essential role in the development and production of new materials for industry, especially electronic materials. The role of metalloporphyrins as chemically interactive materials in chemical sensors has interested researchers for a long time (1-4). The rich coordination chemistry of porphyrins is responsible for their use in chemical-sensor... 

The above mechanistic interpretation is in contrast with the one appearing in the coordination chemistry of NO on the very labile Fe(III) porphyrins and hemoproteins, which show water substitution-controlled kinetics at the iron(III) center (22,25). The latter Fe(III) moieties are, however, high-spin systems, whilst the cyano-complexes are low-spin. There is strong experimental evidence to support the dissociative mechanism with the Fe(III)-porphyrins, because the rates are of the same order as the water-exchange reactions measured in these systems (22d). Besides, the Fe(III) centers are less oxidizing than [Fein(CN)5H20]2- (21,25). 

Neutral adducts are limited to the oxo porphyrin derivatives (Section 34.3.5.4.i) and to the uncharacterized [NbOCl2(NO)(MeCN)2] obtained by hydrolysis of [NbCU(NO)(MeCN)2].539 This high stability of the MOX3 (X = Cl, Br) adducts toward reduction probably hinders easy access to such M adducts. The reduction of NbSX3 (X = Q, Br), on the contrary, allowed the development of sub-thiohalide coordination chemistry. 

The axial coordination chemistry of metallohydroporphyrins parallels that of their porphyrin analogues. 

The axial coordination chemistry of metalloazaporphyrins follows the same trend as that of porphyrin complexes, though these areas are little investigated. 

Synthesis and Coordination Chemistry of Noble Metal Porphyrins... 

Nomenclature, Abbreviations, and Coordination Chemistry of Metal Porphyrinates... 

The coordination chemistry of porphyrins can be subdivided in equatorial and axial coordination chemistry as written in Eqs. (1) and (2) and depicted with the coordination types given in Fig. 3, i.e. square-planar A, square-pyramidal B, or distorted-octahedral C the latter is illustrated by formula 1 [7, 8]. 

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