1319211-85-2

Upstream product

• 959157-34-7 (5,10,15-tris(4-tert-butylphenyl)corrolato)copper 
• 7783-99-5 silver(I) nitrite 
• 142-71-2 copper diacetate 
• 7632-00-0 sodium nitrite 
• 959157-34-7 5,10,15-tris[(4-tert-butylphenyl)corrolato]copper(III) 

Downstream Products

• 1319211-89-6 [((NCCHCHC)2(CC₆H₄C(CH₃)3)3(NCC(NO₂)C(NH₂)C)2)Cu] 

Relevant academic research and scientific papers

Copper β-trinitrocorrolates

The β-nitration reaction carried out on the corrole macrocycle has been shown to be extremely regioselective, although the reduced symmetry of the macrocycle could potentially lead to a huge number of possible regioisomers. We recently reported that the careful use of AgNO2/NaNO2 as a nitrating system enabled the achievement in good yields of mono- and dinitro-derivatives on both corrole free base and its copper complex, proving to be an efficient and cost-effective method. In this work, we present a detailed study of the scope of this method using TtBuCorrH3 as a model corrole. A further increase of the oxidant pushes the nitration up to the functionalization of three β-pyrrolic positions, although concomitant decomposition of the macrocycle is also observed. The application of the proven nitration method with a five-fold excess of both silver and sodium nitrites with respect to corrole, afforded the 2,3,17-(NO2)3- TtBuPCorrCu as the main product, in 25% yield, together with traces of another compound identified by X-ray crystallographic analysis as the 3,8,17-(NO 2)3-TtBuPCorrCu isomer. In light of these recent results, we also reinvestigated the characterization of the nitration products obtained from bis-substitution reactions, allowing among others the identification of the copper 3,8-(NO2)2 corrolate.

Amination reaction on copper and germanium β-nitrocorrolates

Copper and germanium complexes of β-substituted nitrocorroles were reacted with 4-amino-4H-1,2,4-triazole to give the corresponding β-amino-β-nitro derivatives, in moderate to good yields. This is the first successful example of a vicarious nucleophilic substitution performed on corrole derivatives, because the same reaction carried out on silver complexes afforded the corresponding 6-azahemiporphycenes by way of corrole ring expansion. The first step of this work is related to the modification of a synthetic protocol for preparation of the β-substituted nitro corroles. The nitration reaction was carried out on a copper corrole using NaNO2 as the primary source of NO2- coupled with AgNO 2 used as oxidant. By variation of the molar ratio of the reagents it was possible to direct the product distribution toward mono- and dinitro derivatives. The reaction between mono- and dinitro derivatives of (TtBuCorrCu) with 4-amino-4H-1,2,4-triazole gave good results, leading to the isolation of 2-(NH2)-3-(NO2)-TtBuCorrCu and 2,18-(NH2) 2-3,17-(NO2)2-TtBuCorrCu in moderate yields. To elucidate factors that influence the reaction, and to highlight the different behavior observed for different metal complex substrates, the electrochemistry of three copper complexes, TtBuPCorrCu, (NO2)TtBuPCorrCu, and (NO2)2TtBuPCorrCu, was studied by cyclic voltammetry and thin-layer UV-visible spectroelectrochemistry. The nitro groups on (NO 2)xTtBuPCorrCu are highly electron-withdrawing, which leads not only to a substantial positive shift of all redox potentials but also to a unique redox behavior and UV-vis spectrum of the singly reduced product as compared to the parent compound, TtBuPCorrCu. Finally, the amination reaction was carried out on a Ge(IV) nitrocorrolate, giving in good yield the 2-amino-3-nitroderivative, which was structurally characterized by single crystal X-ray crystallography.