Information pertaining to the stereochemistry of metalloporphyrins and other tetrapyrroles continues to expand. The present article reviews important developments of this structural chemistry. Detailed updates on the relationship of the structure and physical properties of iron derivatives are given. Metalloporphyrins with unusually high or low oxidation states are reviewed. Surveys of recent work on π-cation radical complexes, bound O2 species, tetrapyrroles with N-substituents, the stereochemistry of ring-reduced tetrapyrroles and a variety of novel species are given. Newly developed data concerning experimental electron density studies are summarized. Detailed reviews of porphyrin-porphyrin (π-π) interactions in the solid state are given. A variety of important conformational aspects of metalloporphyrins and their consequent results on physical properties are presented. Finally, a number of isomorphous series and crystal packing effects in tetrapyrroles have been detailed.

Recent advances in the stereochemistry of metallotetrapyrroles

The role of group 14 element carbene analogues in transition metal chemistry

The Coordination Chemistry of Tin Porphyrin Complexes

Porphyrins are known to coordinate with most of the metallic or pseudo-metallic elements. However, in spite of the large number of isolated metalloporphyrin derivatives, metal-carbon σ-bonded complexes are limited only to the following series: Fe, Ru, Co, Rh, Ir, Ti, Al, Ga, In, Tl, Si, Ge, Sn, and Zn.

Synthesis, electrochemistry, and structural properties of porphyrins with metal-carbon single bonds and metal-metal bonds

A general high-yield synthetic route to the hexacoordinate silicon porphyrin dichloride complexes trans-(Por)SiCl2 {Por = the dianions of octaethylporphyrin (OEP), tetraphenylporphyrin (TPP), and tetrakis(p-(trifluoromethyl)phenyl)porphyrin (TTFP)} is reported. Reacting (Por)SiCl2 with SbF3 and AgOTf produces the corresponding difluoro trans-(Por)SiF2 and bis(triflato) trans-(Por)Si(OTf)2 complexes, respectively. The spectroscopic properties (1H, 19F, and 29Si NMR and visible) of these hexacoordinate silicon compounds are surprisingly insensitive to the electron-donating ability of the porphyrin or the nature of the axial substituents. The nature of the porphyrin and the axial substituent do play a role in the reactivity of these silicon complexes. The strong Si−F bond makes the difluorides stable to hydrolysis and methanolysis. The dichlorides, on the other hand, do undergo hydrolysis and methanolysis, the extent of which is determined by the electronics of the porphyrin ring. The strong electron-donatin...

Substituent Effects on the Spectroscopic Properties and Reactivity of Hexacoordinate Silicon(IV) Porphyrin Complexes

Metal-metal bonds extended over a porphyrin ring. 1. Syntheses of (TPP)SnM(CO)n-1HgM(CO)n and (TPP)InM(CO)n (M(CO)n = Mn(CO)5, Co(CO)4) and x-ray molecular structure analysis of (TPP)SnMn(CO)4HgMn(CO)5.1/2CH2Cl2

Metal-metal bonds extended over a porphyrin ring. 1. syntheses of (tpp)snm(co)n-1hgm(co)n and (tpp)inm(co)n (m(co)n = mn(co)5, co(co)4) and x-ray molecular structure analysis of (tpp)snmn(co)4hgmn(co)5.1/2ch2cl2

Masafumi Goto

Papers

Metal-metal bonds extended over a porphyrin ring. 1. Syntheses of (TPP)SnM(CO)n-1HgM(CO)n and (TPP)InM(CO)n (M(CO)n = Mn(CO)5, Co(CO)4) and x-ray molecular structure analysis of (TPP)SnMn(CO)4HgMn(CO)5.1/2CH2Cl2

Metal-metal bonds extended over a porphyrin ring. 1. syntheses of (tpp)snm(co)n-1hgm(co)n and (tpp)inm(co)n (m(co)n = mn(co)5, co(co)4) and x-ray molecular structure analysis of (tpp)snmn(co)4hgmn(co)5.1/2ch2cl2