Ion-Pair Extraction of Metalloporphyrins into Acetonitrile for Determination of Copper(II) (original) (raw)
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Porphyrins and metalloporphyrins provide an extremely versatile nanometer-sized building block for the control of materials properties. Films, solids and microporous solids have been explored as field-responsive materials (i.e. interactions with applied electric, magnetic or electromagnetic fields) and as 'chemo-responsive' materials (i.e. interactions with other chemical species as sensors or for selective binding or catalysis). Copyright
Halogenation of metalloporphyrins
Russian Journal of Bioorganic Chemistry, 2000
We found that thionyl chloride can chlorinate porphyrin complexes with transient metals (Pd, Ni, or Cu) at the free 13 and meso-positions of the porphyrin macrocycle. A more prolonged or rigorous treatment also causes the chlorination of side alkyl substituents, mainly, methyl groups.
Inorganic Chemistry, 2004
Crystallization and crystal structure analysis of chlorohydrates of either tri-or tetracationic copper porphyrins, namely copper(5,-10,15-tris(N-methyl-pyridinium-4-yl)-20-pyridine-porphyrinato) (1) and copper(5,10,15,20-tetrakis(N-methyl-pyridinium-4-yl)-porphyrinato), respectively, have been performed. Two crystalline forms, 2 and 3, of the latter have been obtained under different preparation conditions. A novel kind of slipped stack chains of these cationic porphyrins has been detected. The pronounced saddle conformation of the porphyrin reveals π-like interactions between the peripheral pyrrole C b −C b "double bond" and the metal center. DFT calculations on the isolated porphyrins clearly show the HOMO orbitals with the correct topology to yield a bonding interaction among the stacked porphyrin units. To our knowledge, a slipped stack chain of positively charged porphyrins has never been previously reported, if the arrangement of faced units of monocationic metalloporphyrins or phthalocyanins is excluded.
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Porphyrins and related macrocycles provide an extremely versatile synthetic base for a variety of materials applications. The exploration of metalloporphyrin assemblies as building blocks for tailored materials properties has found rapid growth during the past decade 1 . In this chapter, we shall review the rather diverse applications of porphyrins to materials chemistry and try to draw the common threads between these topics as possible.
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The porphyrins, naturally occurring macrocyclic compounds, have, in the last 10 years, gained increasing interest in analytical chemistry. This review based on 123 original literature references, mostly published in the 1990s, presents catalytic applications of metalloporphyrins in electroanalysis as electroactive agents in ion selective membranes, as unique reagents in spectrophotometry and as new stationary phases offering unusual resolution in HPLC. The collected data are also presented in four tables.
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The metalloporphyrin formation reaction is one of the important processes from both analytical and bioinorganic points of view. The large molar absorption coefficient and very high stability of the metalloporphyrins are very useful for the highly sensitive analysis of trace amounts of metal ions, and the size selectivity of the porphyrins is valuable for the separation of various kinds of metal ions. 1-7 A variety of metalloporphyrin formation rates are also applicable for the kinetic analysis of metal ions. 8,9 On the other hand, kinetic studies of metalloporphyrin formation are indispensable in order to understand in vivo metal 917
Talanta, 2004
The reaction of 3,8,13,18-tetramethyl-21H,23H-porphine-2,7,12,17-tetrapropionic acid or coproporphyrin-I (CPI) with the elements of 11 group have been studied. CPI is an anionic porphyrin that slowly reacts with copper ion to form Cu II CPI and with silver ions to form Ag II CPI, Ag III CPI complexes and colloidal silver. Gold ions do not form complexes with CPI, but, in the main, colloidal gold and some CPI-N-oxide. The kinetics of the reactions with copper and silver were spectrophotometerically studied and the rate constants were calculated. The identification and characterization of this water-soluble anionic porphyrin and its metal complexes have been performed by electrospray mass spectrometry (ESI-MS) that proved to be an excellent method for these determinations. The multiple charged parent ions for metal free ligand and their metal complexes were identified.
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