Manganese corroles

Fig. 6 The varied reactivity of chromium and manganese corrole complexes...

Gross Z, Golubkov G, Simkhovich L (2000) Epoxidation catalysis by a manganese corrole and isolation of an oxomanganese(V) corrole. Angew Chem Int Ed 39 4045 1047... 

Shen J, El Ojaimi M, Chkounda M, Gros CP, Barbe JM, Shao J, Guilard R, Kadish KM (2008) Solvent, anion, and structural effects on the redox potentials and UV-visible spectral properties of mononuclear manganese corroles. Inorg Chem 47 7717-7727... 

Recent developments in manganese corrole chemistry 13CCR1306. Reductive N—N coupling of NO molecules on transition metal heme-based complexes leading to N2O 12CCR468. 

In 2006, Abu-Omar reported on stop-flow studies of the reactions of the soluble ArlNTs reagent ( Ar=ort/i )- BuS02C6H4), an analogue of the soluble iodosylarene described above, with the manganese corrole complex [(tpfc)Mn (EtOAc)] (tpfc=5,10,15-tris(pentafluorophenyl)corrole (Scheme 19) [82]. [(tpfc) Mn(EtOAc)] can catalyze the reaction of PhINTs with styrene to form aziridines. In this study, an initial adduct of the ArlNTs with Mn corrole leads to a detectable mono-adduct [(tpfc)Mn N(Ts)FAr ] (Scheme 16). The initially formed adduct then loses ArI to form an isolable Mn imino complex [(tpfc)Mn(=NTs)]. This imino complex, however, is not the active catalyst for imino transfer to olefins. 

Zdilla MJ, Abu-Omar MM (2006) Mechanism of catalytic aziridination with manganese corrole the often postulated high-valent Mn(V) imido is not the group transfer reagent. J Am Chem Soc 128(51) 16971-16979... 

The first reports on iron-catalyzed aziridinations date back to 1984, when Mansuy et al. reported that iron and manganese porphyrin catalysts were able to transfer a nitrene moiety on to alkenes [90]. They used iminoiodinanes PhIN=R (R = tosyl) as the nitrene source. However, yields remained low (up to 55% for styrene aziridination). It was suggested that the active intermediate formed during the reaction was an Fev=NTs complex and that this complex would transfer the NTs moiety to the alkene [91-93]. However, the catalytic performance was hampered by the rapid iron-catalyzed decomposition of PhI=NTs into iodobenzene and sulfonamide. Other reports on aziridination reactions with iron porphyrins or corroles and nitrene sources such as bromamine-T or chloramine-T have been published [94], An asymmetric variant was presented by Marchon and coworkers [95]. Biomimetic systems such as those mentioned above will be dealt with elsewhere. 

The early collaboration between Gray and Bendix, like that between Ballhausen and Gray, involved the development of electronic and molecular descriptions of novel transition metal complexes. During his fellowship at Caltech, Bendix examined the manganese [22, 23] and gallium [24] complexes of a class of porphyrinoid macrocycles known as corroles [25-28]. Corroles were once difficult to prepare in the laboratory, but they have become more accessible due to the development of new syntheses [29-37]. According to a Scifinder [38] search performed on June 5, 2011,... 

Bendix J, Gray HB, Golubkov G, Gross Z (2000) High-field (high-frequency) EPR spectroscopy and structural characterization of a novel manganese(III) corrole. Chem Commun 19 1957-1958... 

Edwards NY, Eikey RA, Loring MI, Abu-Omar MM (2005) High-valent imido complexes of manganese and chromium corroles. Inorg Chem 44 3700-3708... 

Ou Z, Erben C, Autret M, Will S, Rosen D, Lex J, Vogel E, Kadish KM (2005) Manganese (III) and manganese(IV) corroles synthesis, spectroscopic, electrochemical, and X-ray structural characterization. J Porphyr Phthalocyanines 9 398 1-12... 

Liu HY, Yam F, Xie YT, Li XY, Chang CK (2009) A bulky bis-pocket manganese(V)-oxo corrole complex observation of oxygen atom transfer between triply bonded MnVtO and alkene. J Am Chem Soc 131 12890-12891... 

Kumar A, Goldberg I, Botoshansky M, Buchman Y, Gross Z (2010) Oxygen atom transfer reactions from isolated (oxo)manganese(V) corroles to sulfides. J Am Chem Soc 132 15233-15245... 

Golubkov G, Gross Z (2005) Nitrogen atom transfer between manganese complexes of salen, porphyrin, and corrole and characterization of a (nitrido)manganese(VI) corrole. J Am Chem... 

Saltsman I, Goldberg I, Gross Z (2010) Water-soluble manganese(III) corroles and corresponding (nitrido)manganese(V) complexes. J Porphyr Phthalocyanines 14 615-620... 

Abu-Omar MM (2011) High-valent iron and manganese complexes of corrole and porphyrin in atom transfer and dioxygen evolving catalysis. Dalton Trans 40 3435-3444... 

Steene E, Wondimagegn T, Ghosh A (2001) Electrochemical and electronic absorption spectroscopic studies of substituent effects in iron(IV) and manganese(IV) corroles do the compounds feature high-valent metal centers or noninnocent corrole ligands Implications for peroxidase compound I and II intermediates. J Phys Chem B 105 11406-11413... 

What is the difference between the manganese porphyrin and corrole analogues of cytochrome P450 s compound 1 Chem. Eur. J. 7, 4954 960. 

Epoxidation of alkenes with iodosylbenzene can be effectively catalyzed by the analogous salen or chiral Schiff base complexes of manganese(in), ruthenium(II), or ruthenium(III). For example, the oxidation of indene with iodosylbenzene in the presence of (/ ,5)-Mn-salen complexes as catalysts affords the respective (15,2/ )-epoxyindane in good yield with 91-96% ee [704]. Additional examples include epoxidation of alkenes with iodosylbenzene catalyzed by various metalloporphyrins [705-709], corrole metal complexes, ruthenium-pyridinedicarboxylate complexes of terpyridine and chiral bis(oxazoUnyl)pyridine [710,711]. 

Figure 10.12 2,17-Bis-sulfonato-5,10,15-tri(pentafluorophenyl)corrole manganese complex 14 [59,60], tetrakis(sulfonato) phthalocyanin copper complex 15 [61], and meso-tetrakis (p-carboxyphenyl)-porphyrln manganese complex 16 [62].

Metal-catalysts that enable the direct transfer of an Ni-moiety from chloramine-T to alkenes with moderate efficiencies include metalloporphyrinoids. For example, in 2001, Simkhovich and Gross reported that iron (IV) corrole 21 (Scheme 2.29) catalyzed olefin aziridination with chloramine-T [44]. The use of porphyrine complexes of iron [Fe(TPP)Cl] and cobalt [Co(TDClPP)] in the presence of bromamine-T also allows for aziridinating a wide variety of alkenes [45,46]. A recyclable polymer-supported manganese (II) complex, which is readily prepared from chloromethy-lated poly(styrene-divinylbenzene) (PS-DVB) in two steps, transfers an Ni unit from bromamine-T to aliphatic alkenes in a heterogeneous system [47]. 

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