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• 563-63-3 silver(I) acetate 
• 7783-99-5 silver(I) nitrite 

Relevant academic research and scientific papers

Observations on the Mechanochemical Insertion of Zinc(II), Copper(II), Magnesium(II), and Select Other Metal(II) Ions into Porphyrins

Building on a proof of concept study that showed the possibility of the mechanochemical insertion of some M(II) metals into meso-tetraphenylporphyrin using a ball mill as an alternative to traditional solution-based methods, we present here a detailed study of the influence of the many experimental variables on the reaction outcome performed in a planetary mill. Using primarily the mechanochemical zinc, copper, and magnesium insertion reactions, the scope and limits of the type of porphyrins (electron-rich or electron-poor meso-tetraarylporphyrins, synthetic or naturally occurring octaalkylporphyrins, and meso-triphenylcorrole) and metal ion sources suitable for this metal insertion modality were determined. We demonstrate the influence of the experimental metal insertion parameters, such as ball mill speed and reaction time, and investigated the often surprising roles of a variety of grinding agents. Also, the mechanochemical reaction conditions that remove zinc from a zinc porphyrin complex or exchange it for copper were studied. Using some standardized conditions, we also screened the feasibility of a number of other metal(II) insertion reactions (VO, Ni, Fe, Co, Ag, Cd, Pd, Pt, Pb). The underlying factors determining the rates of the insertion reactions were found to be complex and not always readily predictable. Some findings of fundamental significance for the mechanistic understanding of the mechanochemical insertion of metal ions into porphyrins are highlighted. Particularly the mechanochemical insertion of Mg(II) is a mild alternative to established solution methods. The work provides a baseline from which the practitioner may start to evaluate the mechanochemical metal insertion into porphyrins using a planetary ball mill.

Functionalization of corroles: The nitration reaction

The reaction of meso-triarylcorroles with AgNO2 proceeds with concomitant metalation and peripheral substitution to give the corresponding nitro-substituted silver(III) corrole complex. The substitution is highly regioselective, giving only the

Synthesis and structure of [meso-triarylcorrolato]silver(III)

An efficient meso-triarylcorrole synthesis is detailed, and the formation and spectroscopic properties of their diamagnetic square-planar d8 AG(III) complexes are described. The spectroscopic properties of the [corrolato]-AG(III) complexes are contrasted with those of the corresponding [porphyrinato] Ag(II) complexes. The oxidation state of the central metal in the corrolato complexes was inferred from their diamagnetic NMR spectra, from X-ray photoelectron spectroscopy measurements, and by single-crystal X-ray diffractometry of the [meso-tetra-p-tolylcorrolato]-silver(III) complex TTCAgIII, as its toluene solvate (crystal data for C40H29N4Ag·C7 H8: monoclinic space group C2/c with a = 21.4679(19) A, b = 20.7606(19) A, c = 16.0122(11) A, β = 93.700(4)°, V = 7121.5(10) A3, Z = 8, R = 0.0453, and Rw = 0.1131). The conformation of the corrolato ligand in the complex is slightly saddled. The AG(III) complexes are without precedent in the coordination chemistry of corroles. The Ag(III) complexes underline the ability of meso-triarylcorroles to stabilize higher oxidation states as compared to the corresponding mesotetraarylporphyrinato complexes.