Reactivity of iron(II) 5,10,15,20-tetraaryl-21-oxaporphyrin with arylmagnesium bromide: formation of paramagnetic six-coordinate complexes with two axial aryl groups

Inorganic Chemistry
Miłosz Pawlicki, Lechosław Latos-Grazyński

Abstract

Coordination of sigma-aryl carbanions by chloroiron(II) 5,20-ditolyl-10,15-diphenyl-21-oxaporphyrin (ODTDPP)Fe(II)Cl has been followed by (1)H NMR spectroscopy. Addition of pentafluorophenyl Grignard reagent (C(6)F(5))MgBr to the toluene solution of (ODTDPP)Fe(II)Cl in the absence of dioxygen at 205 K resulted in the formation of the high-spin (ODTDPP)Fe(II)(C(6)F(5)). The titration of (ODTDPP)Fe(II)Cl with a solution of (C(6)H(5))MgBr carried at 205 K yields a rare six-coordinate species which binds two sigma-aryl ligands [(ODTDPP)Fe(II)(C(6)H(5))(2)](-). Warming of the [(ODTDPP)Fe(II)(C(6)H(5))(2)](-) solution above 270 K results in the decomposition to mono-sigma-phenyliron species (ODTDPP)Fe(II)(C(6)H(5)). Controlled oxidation of [(ODTDPP)Fe(II)(C(6)H(5))(2)](-) with Br(2) affords (ODTDPP)Fe(III)(C(6)H(5))Br, which demonstrates a typical (1)H NMR pattern of low-spin sigma-aryl iron(III) porphyrin. The considered oxidation mechanism involves the (ODTDPP)Fe(III)(C(6)H(5))(2) species, which is readily reduced to the iron(I) 21-oxaporphyrin, followed by oxidation with Br(2) and replacement of one bromide anion by aryl substituent. The (1)H NMR spectra of paramagnetic iron complexes have been examined in detail. Functional group...Continue Reading

References

Aug 23, 2002·Chemical Communications : Chem Comm·Chen-Hsiung HungShie-Ming Peng
Oct 29, 2002·Inorganic Chemistry·Miłosz Pawlicki, Lechosław Latos-Grazyński
Apr 1, 2004·Journal of the American Chemical Society·Krystyna RachlewiczLechosław Latos-Grazyński
Feb 1, 1997·Chemistry : a European Journal·P J ChmielewskiA L Balch

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Citations

Mar 28, 2006·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Miłosz Pawlicki, Lechosław Latos-Grazyński
Dec 21, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Martin BröringSilke Köhler
Sep 12, 2006·Inorganic Chemistry·Radomir MyśliborskiLechosław Latos-Grazyński
Jul 15, 2009·Inorganic Chemistry·Anna Berlicka, Lechosław Latos-Grazyński
Nov 5, 2016·Chemical Reviews·Tamal ChatterjeeMangalampalli Ravikanth

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