Mixed metalloporphyrins

Stultz. E. Ng. Y.-F. Scott, S.M. Sanders. J.K.M. Amplification of a cyclic mixed-metalloporphyrin tetranier from a dynamic combinatorial library through orthogonal metal coordination. Chem. Commun. 2002. 524-525. 

The qualitative stabihty constants of metalloporphyrins are summarized in Table 1. The metals classified in class I produce the most stable metalloporphyrins and the demetalation reaction does not proceed smoothly even under concentrated sulfuric acid condition. The incorporated metals classified in classes 11 and III are removed using mild acids such as hydrochloric acid. Calcium classified in class V is removed by (the pH of) water. The mixed cyclization reactions afford the heterometalated CPO, and the acid treatment of the CPO obtained produces the CPO containing 2HPor moiety. Further treatment of the metal salt classified in a class lower than that of the unremoved metal(s), which is classified in a class higher in Table 1, produces another heterometalated CPO. Representative examples are summarized in Fig. 5 [25]. The initial cyclization reaction is carried out by using Ru (CO)Por 6, the metal of which is classified in class 1, and ZnPor 5, clas-... 

Of considerable interest was the demonstration that metalloporphyrins and the like can be used as nonmetallic catalysts in electrochemical reactions, nourishing hopes that in the future, expensive platinum catalysts could be replaced. Starting in 1968, dimensionally stable electrodes with a catalyst prepared from the mixed oxides of titanium and ruthenium found widespread use in the chlorine industry. 

Most studies of ORR catalysis by metalloporphyrins have been carried out using water-insoluble catalysts absorbed on a graphite electrode in contact with aqueous solution. In a limited number of cases, four other approaches have been used catalysts imbedded in an inert film (i.e., Nafion or lipid) on the electrode surface self-assembled monolayers of catalysts catalysts in aqueous or mixed organic/aqueous solutions in contact with an electrode and catalysis in mixed aqueous/organic medium using... 

As a result of strong electronic interactions between the two metalloporphyrin units, there is a substantial uncertainty in assigning oxidation states in mixed-valence group 2 complexes of redox-active metals, such as Co. Thus, although reduced neutral C02 derivatives can be reasonably well described as those of Co the location (metal versus porphyrin) of the electron hole(s) in the singly and doubly oxidized derivatives is not known definitively, and may be very sensitive to the medium [LeMest et al., 1996, 1997]. For example, in benzonitrile, the UV-vis spectmm of [(FTF4)Co2]" ... 

Sanders (14) has exploited the strong and selective coordination of phosphine donor groups to Ru(II) to construct hetero-dimetallic porphyrin dimers (17, Fig. 5). An alkyne-phosphine moiety introduced on the periphery of a free base or metalloporphyrin (M = Zn or Ni) spontaneously coordinates to a Ru(II)(CO) porphyrin when the two porphyrins are mixed in a 1 1 ratio. Coordination is characterized by a downfield shift of the 31P resonance (A<531P = 19 ppm). There is no evidence of self-coordination of the zinc porphyrin at 10 6 m in toluene, there is no shift in the Soret band in the UV-Vis absorption spectrum. The Ni-Ru dimer was observed by MALDI-TOF mass spectrometry. Heating the Ru(II)CO porphyrin with 2 equivalents of the phosphine porphyrins led to quantitative formation of trimeric assemblies. 

The axial coordination of metalloporphyrins to a pyridyl ligand was successfully exploited by two groups to produce porphyrin-stoppered rotaxanes. Sanders (48) assembled a rotaxane by simply mixing the constituent parts. Zn(II), Ru(II)CO, and Rh(II)Cl porphyrins were used as stoppers. Branda (49) reported the stoppering of a pseudorotaxane by adding two equivalents of a Ru(II)CO porphyrin that coordinated to... 

The hyper type and the hypso type may occur in mixed versions (61). The hypso type has not always been recognized as an individual spectral type by other authors, and, concomitantly, the importance of metal-to-porphyrin backbonding has been neglected (46, 48). The present scheme cannot explain why some large alkaline earth cations cause bathochromic shifts as long as a definite structural characterization of these metalloporphyrins is missing (20-22). 

Asymmetrical, Mixed Bisporphyrinates - The synthetic paths (paths — f, — j, k) preclude an easy synthesis of heterobimetallic complexes like RuOs(OEP)2. Such complexes were obtained in pure forms by stepwise metallation of H2(DPB) to RuOs(DPB) [232]. Separation of a mixture of [Ru(OEP)]2, [Ru(OETAP)]2, and Ru2(OETAPXOEP) was achieved by stepwise oxidation of these bis-metalloporphyrins using AgBF4 in toluene when first [Ru(OEP)]2BF4 and then [Ru2(OETAP)(OEP)]BF4 precipitated. The latter was then reduced with cobaltocene to give pure Ru2(OETAP)(OEP) [233]. 

Intestinal absorption studies of Mn-MP were undertaken in an effort to assess the viability of the metalloporphyrin as an oral hepatobiliary agent [101, 102]. Mixed micelles of Mn-MP complexed with monoolein and taurocholate were administered to rats, resulting in liver image enhancement 68% above baseline levels six hours after administration [101]. In pigs, the mixed micelle preparation showed variable enhancement over 24 hours. Observation that Mn-MP interacts with oleic acid vesicles [103] led to investigations of the effect of oleic acid on the absorption rate of Mn-MP from the small bowel into the circulatory system [102,104]. The increase in absorption of the complex was mediated by a decrease in the relaxivity of the metalloporphyrin resulting from the interaction with the lipid vesicles. 

In such a case, it is not possible to describe normal modes in terms of one local mode such as v(C—C), v(C—N) or v(C—O). Instead, they are described as a mixing of these local modes ( vibrational coupling ). As will be shown in Chapter 4, Section 4.1.2, examples of such vibrational couplings are seen in metalloporphyrins and peptides. 

There are several photocatalysts mimicking hydrogenase activity that are not based on metalloporphyrin systems. Among them there are mixed-valence complexes of rhodium or iridium, [41] as well as complex systems encompassing photosensitizers (eg ruthenium complexes) attached to a catalytic bimetallic centre [43], The design of more sophisticated systems approaches that of photosynthetic processes [44],... 

A related series of mixed-metal face to face porphyrin dimers (192) has been studied by Collman et al.506 A motivation for obtaining these species has been their potential use as redox catalysts for such reactions as the four-electron reduction of 02 to H20 via H202. It was hoped that the orientation of two cofacial metalloporphyrins in a manner which permits the concerted interaction of both metals with dioxygen may promote the above redox reaction. Such a result was obtained for the Co11 /Co" dimer which is an effective catalyst for the reduction of dioxygen electrochemic-ally.507 However for most of the mixed-metal dimers, including a Con/Mnn species, the second metal was found to be catalytically inert with the redox behaviour of the dimer being similar to that of the monomeric cobalt porphyrin. However the nature of the second metal ion has some influence on the potential at which the cobalt centre is reduced. 

The present paper describes the mechanism of porphyrin metalation in the presence of catalyst with special emphasis on the reaction intermediates including heterodinuclear metalloporphyrin, mixed-valence metalloporphyrin, and sandwich-metalloporphyrin with 18-crown-6. 

---