Metalloporphyrins synthesis

Metalloprotein redox reactions. (L. E. Bennett, Progr. Inorg. Chem., 1973, 18, 1). Novel metalloporphyrins-synthesis and implications. (D. Ostfield and M. Tsutsui, Accounts Chem. Res., 1974, 7, 52). 

Bhyrappa P, Young JK, Moore JS, Suslick KS. Dendrimer-Metalloporphyrins Synthesis and catalysis. J Am Chem Soc 1996 118 5708-11. 

C. J. Carrano and M. Tsutsui. Unusual metalloporphyrins Synthesis and properties of a dimetallic boron prophyrin complex. /. Coordination Chem., 1977, 7, 125. 

Metallacyclopentanes, 3,4-dimethylene-synthesis, 1, 669 Metallacyclopentan-2-ones synthesis, 1, 669 Metallacyclopentenes synthesis, 1, 670 Metallafluorenes synthesis, 1, 671 Metallaindanes synthesis, 1, 670 Metallaindenes synthesis, 1, 670, 671 Metallaxanthenes synthesis, 1, 671 Metalloporphyrins anions, 4, 398 demetallation, 4, 389... 

Simplifying the synthesis of the catalysts (e.g., the highly optimized convergent synthesis of monometallic series 2 metalloporphyrins required between 14 and 17 steps [Collman et al., 2002d]—FeAc (Fig. 18.21a) is available in 7 steps). 

DMPO has been used in the synthesis of the first metalloporphyrin nitrone complex (443). On the basis of nitrone ligands (L) (Scheme 2.81) the synthesis of rhodium (I) carbonyl complexes of the type [Rh(CO)2ClL] was carried out. These complexes are used as effective catalysts of methanol carbonylation into acetic acid and its ester (444). 

The electrosynthesis of metalloporphyrins which contain a metal-carbon a-bond is reviewed in this paper. The electron transfer mechanisms of a-bonded rhodium, cobalt, germanium, and silicon porphyrin complexes were also determined on the basis of voltammetric measurements and controlled-potential electrooxidation/reduction. The four described electrochemical systems demonstrate the versatility and selectivity of electrochemical methods for the synthesis and characterization of metal-carbon o-bonded metalloporphyrins. The reactions between rhodium and cobalt metalloporphyrins and the commonly used CH2CI2 is also discussed. 

Metalloporphyrins containing a metal-carbon a-bond are currently limited to complexes with eight different transition metals (Ti, Ni, Fe, Ru, Co, Rh, Ir and In) and seven different non-transition metals (Al, Ga, In, Tl, Si, Ge, and Sn). These compounds have been the subject of several recent reviews(1-33 which have discussed their synthesis and physicochemical properties. 

The synthesis of metalloporphyrins which contain a metal-carbon a-bond can be accomplished by a number of different methods(l,2). One common synthetic method involves reaction of a Grignardreagent or alkyl(aryl) lithium with (P)MX or (PMX)2 where P is the dianion of a porphyrin macrocycle and X is a halide or pseudohalide. Another common synthetic technique involves reaction of a chemically or electrochemically generated low valent metalloporphyrin with an alkyl or aryl halide. This latter technique is similar to methods described in this paper for electrosynthesis of cobalt and rhodium a-bonded complexes. However, the prevailing mechanisms and the chemical reactions... 

In summary, the four chemical systems described in this paper demonstrate the versatility and selectivity of electrochemical methods for synthesis and characterization of metal-carbon a-bonded metalloporphyrins. The described rhodium and cobalt systems demonstrate significant differences with respect to their formation, stability and to some extend, reactivity of the low valent species. On the other hand, properties of the electroche-mically generated mono-alkyl or mono-aryl germanium and silicon systems are similar to each other. 

The metalloporphyrins were very intensively studied and their properties are presented in monographs [140-142]. The synthesis and properties of Zn(II)-por-phyrin complexes are presented in selected works [143-154]. 

Takeuchi D, Watanabe Y, Aida T, Inoue S (1995) Maclomolecules 28 651 Recent reviews (a) Aida T (1994) Prog Polym Sci 19 469 (b) Inoue S, Aida T (1998) Controlled polymer synthesis with metalloporphyrins. In Vogl O, Hatada K (eds) Molecular design of polymeric materials. Dekker, New York, in press (a) Kuroki M, Watanabe T, Aida T, Inoue S (1991) J Am Chem Soc 113 5903 (b) Sugimoto H, Kuroki M, Watanabe T, Kawamura C,Aida T, Inoue S (1993) Macromolecules 26 3403 (c) Sugimoto H,AidaT, Inoue S (1994) Macromolecules 27 3672 (d) Sugimoto H, Kawamura C, Kuroki M, Aida T, Inoue S (1994) Macromolecules 27 2013 (e) Akatsuka M, Aida T, Inoue S (1994) Macromolecules 27 2820 Inoue, S, Aida T (1994) Chem tech 24 28... 

The use of appropriate analytical standards is important for successful chromatographic separation, identification, and quantification of chlorophyll derivatives. While chlorophyll a and b derivatives are readily available commercially (Sigma-Aldrich) both metal-free pheophytins and metalloporphyrin analogs such as Cu2+ and Zn2+ pheophytins are not. In most instances, these derivatives must be prepared from the parent Mg-chlorophyl standards prior to use. These simple synthesis techniques are based on the work of Schwartz (1984) and are to be utilized for the rapid and efficient preparation of metal-free, Cu2+ and Zn2+ pheophytin derivatives in quantities appropriate only for analytical implementation. 

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