Paper
Reactions of Nickel(II) 2-Aza-5,10,15,20-tetraphenyl-21- carbaporphyrin with Methyl Iodide. The First Structural Characterization of a Paramagnetic Organometallic Nickel(II) Complex†
Published Jun 19, 1996 · P. Chmielewski, L. Latos‐Grażyński, T. Głowiak
Journal of the American Chemical Society
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Abstract
The methylation of a nickel(II) complex (CTPP)NiII of 2-aza-5,10,15,20-tetraphenyl-21-carbaporphyrin (CTPPH2) with the mild methylating agent methyl iodide yields novel stable organonickel(II) complexes: diamagnetic (21-CH3TPP)NiII and two scarce paramagnetic species (2-NH-21-CH3CTPP)NiIIX and (2-NCH3-21-CH3CTPP)NiIIX (X = Cl, I). The demetalation procedure resulted in isolation of two 21-carbaporphyrin derivatives, methylated at the internal C(21) carbon atom, i.e., 2-aza-5,10,15,20-tetraphenyl-21-methyl-21-carbaporphyrin (21-CH3-CTPPH2) and 2-aza-2-methyl-5,10,15,20-tetraphenyl-21-methyl-21-carbaporphyrin (2-NCH3-21-CH3CTPPH). The methylation mechanism involves the oxidative addition of the methyl cation to the carbaporphyrin C(21) activated due to Ni−C coordination. These C-methylated macrocycles preserve their coordinating properties as the remetalation processes have been carried out. The reversible concerted addition of HX converts the diamagnetic (21-CH3TPP)NiII into the paramagnetic (2-NH-21-CH3C...
Methyl iodide methylation of nickel(II) complexes with 2-aza-5,10,15,20-tetraphenyl-21-carbaporphyrin produces novel organometallic nickel(II) complexes, including diamagnetic (21-
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