Metalloporphyrins porphyrin bridge

Metalloporphyrins have been used for epoxidation and hydroxylation [5.53] and a phosphine-rhodium complex for isomerization and hydrogenation [5.54]. Cytochrome P-450 model systems are represented by a porphyrin-bridged cyclophane [5.55a], macrobicyclic transition metal cyclidenes [5.55b] or /3-cyclodextrin-linked porphyrin complexes [5.55c] that may bind substrates and perform oxygenation reactions on them. A cyclodextrin connected to a coenzyme B12 unit forms a potential enzyme-coenzyme mimic [5.56]. Recognition directed, specific DNA cleavage... 

One-electron oxidation of the vinylidene complex transforms it from an Fe=C axially symmetric Fe(ll) carbene to an Fe(lll) complex where the vinylidene carbon bridges between iron and a pyrrole nitrogen. Cobalt and nickel porphyrin carbene complexes adopt this latter structure, with the carbene fragment formally inserted into the metal-nitrogen bond. The difference between the two types of metalloporphyrin carbene, and the conversion of one type to the other by oxidation in the case of iron, has been considered in a theoretical study. The comparison is especially interesting for the iron(ll) and cobalt(lll) carbene complexes Fe(Por)CR2 and Co(Por)(CR2) which both contain metal centers yet adopt... 

Metalloporphyrins, MP, represent derivatives of porphyrin, P, in which four pyrrole fragments are bound together by methine bridges (Fig. 13). The diversity of porphyrins is due to the possibility of variation for substituents R in the periphery of the porphyrin ring. A typical optical spectrum of a P solution is presented in Fig. 14. One can point out quite a number of characteristic bands in it. The most intensive short-wave peak in the P absorption spectrum (/max 400 nm) corresponds to the transition S0 -+ S2 and is referred to as Soret band. The extinction coefficient of this band is very large, as a rule, and amounts to 10 -106 M 1 cm-1. The less intensive long-wave bands of P absorption correspond to the S0 - Sx transition (bands I-IV in Fig. 14). Complexation with the metal results in a rise of the symmetry of the molecule, due to which MP molecules have only two bands in the long-wave part of the absorption spectra. Most of the metalloporphyrins are characterized by intense luminescence. The time of MP fluorescence decay (transition Si - S0) is short and amounts to 10"8 to 10 9 s. Besides the transition... 

Hydrodemetallation pathways for Ni-etioporphyrin and Ni-tetra(3-methylphenyl)porphyrin are shown in Fig. 20. Both are characterized by a sequential hydrogenation-hydrogenolysis global mechanism, but important differences are apparent. Ware and Wei (1985a) rationalized the differences in porphyrin reactivity on the basis of porphyrin molecular structure. Structural differences on the periphery of the metalloporphyrin, in particular the substituent groups at the /3-pyrrolic and methine bridge... 

The bidentate bis(diphenylphosphino) alkane ligands (entries 8 and 42) are not capable of forcing the porphyrin ligand to leave the equatorial position of noble metal porphyrins. Either two bidentates are bound in a monodentate fashion, or a bidentate bridges two metalloporphyrin entities. 

As a leading example for short-spaced dyads, a n-n stacked porphyrin-fullerene dyad (ZnP-Ceo) 21 should be mentioned, which was probed in light of their electron transfer and back electron transfer dynamics [361, 362], The close van der Waals contact ( 3.0A) is responsible for pronounced electronic interactions in the ground state between the two 7t-chromophores. For example, the ZnP Soret-and Q-bands in the n-n stacked dyad 21 show a bathochromic shift and lower extinction coefficients compared to free ZnP [361], In the n-n stacked dyad 21 the linkage of the two bridging units occurs in the trans-2 position at the fullerene. A charge-separated radical pair evolves from a rapid intramolecular electron transfer k 35 ps) between the photoexcited metalloporphyrin and the fullerene core in a variety of solvents (i.e., ranging from toluene to benzonitrile). Remarkably, the lifetimes in tetrahydrofuran (t = 385 ps) and DCM (t = 122 ps) are markedly increased relative to the more polar solvents dichloromethane (r = 61 ps) and benzonitrile (t = 38 ps) [362]. This dependency prompts to an important conclusion ... 

Woodward has pointed out that porphyrins contain pyrrole units that are on average one half of an electron away from a stable 6-ji-electron configuration [Woodward (214)]. From the presumed tendency to become aromatic pyrrole units one can deduce a metalloporphyrin resonance structure like (VIII), where the methine bridge carbons have lost n-... 

Although this article deals with electron transfers with metalloporphyrins and generally does not cover the chemical reactions of the porphyrin ligand, it is felt that one exception has to be made and that the protonation of the methine bridges of porphyrin n anions should be discussed. This reaction invariably occurs when the reduction of porphyrins is carried out in protic media and is usually fully reversible with a rise in the redox potential of the solution, very much like electron addition and removal [Cfoss (35), Inhoffen (99, 101, 102, 103), Kiselev (113), Mauzerall (129, 130), Peychal-Heiling (147, 148), Seely (156), Shablya (157), Shulga (158), Sidorov (159), Woodward (213, 214)]. 

Single-electron oxidation of the metalloporphyrins 9 (e.g. by halogens or electrochemically) leads to the formation of radical cations. These undergo addition with nucleophiles at a methine bridge and, after acid demetalation, yield monosubstituted porphyrins 10 [18] ... 

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