87607-70-3Relevant academic research and scientific papers
Extended structure of indium(III) protoporphyrin IX acetate mimics dimer structure of hematin anhydride
Dodd, Erin L.,Bohle, D. Scott
, p. 36 - 42 (2016)
A complex of indium(III) protoporphyrin IX acetate was prepared and characterized crystallographically as its pyridine solvate. The structure of the 5-coordinate In complex is dimeric through a strong bridging hydrogen bond between the propionic acid group of one porphyrin unit and the carbonyl of the In-bound acetate, leading to a structure that mimics the reciprocal dimer structure of the malaria pigment hemozoin with an expanded frame. Inter-dimer π-stacking and hydrogen bonding interactions of the propionic acid groups are the dominant structural features. This result, following the report of reciprocal dimers of gallium(III) protoporphyrin IX species, indicates that this is a common motif for metalloprotoporphyrin IX species.
Single hydroxo-bridged group 13 metalloporphyrin dimers: Solution studies and solid-state structures
Munro, Orde Q.,Coutsolelos, Athanassios G.,Cheng, Beisong,Scheidt, W. Robert
, p. 969 - 989 (2019/08/20)
The syntheses of indium, gallium and aluminum porphyrin dimers with a single hydroxo-bridge, {[M(Porph)]2(OH)}+, are described. Emphasis is given to indium and gallium derivatives. The X-ray structures for { [Ga(OEP)]2(OH)} ClO4 and { [In(OEP)]2(OH)} ClO4 (two forms) are presented. The dimeric molecules can be synthesized by the acid-treatment of the corresponding hydroxo-ligated monomeric complexes [M(OEP)(OH)] and [M(TPP)(OH)]. The nature of the starting material (the hydroxo-ligated monomer) was first suggested by IR spectroscopy and further proved by proton-deuterium exchange followed by 1H NMR spectroscopy. The structure of a monomeric indium hydroxide complex, [In(OEP)(OH)], is also presented. The synthesis of the dimer for all metals can be monitored by UV-vis spectroscopy, which clearly demonstrates that a blue-shift of the Soret band accompanies formation of the dimer from the monomer. A strong π-πinteraction between the two porphyrin rings of these μ-hydroxo-bridged dimers is confirmed both by solution state studies (1H NMR and UV-vis spectroscopy) and the X-ray structures of { [M(OEP)]2(OH)} ClO4 (M = In, Ga). In addition, exposure of methylene chloride solutions of these bridged complexes to white light afforded the corresponding chloro derivatives, [M(Porph)Cl]. The stereochemistry of a range of μ-hydroxo dimers is discussed and DFT simulations at the HSEH1PBE/SDD level of theory provide suitable structural models and further electronic structure insights on selected [Ga(Porph)(OH)] and { [Ga(Porph)]2(OH)}+ derivatives.
MOLECULAR CARTESIAN-COORDINATE PLATFORMS
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Page/Page column 71-72, (2012/10/18)
A compound of formula MOL -M-L, wherein M is a 5 or 6-coordinate metal, L is a bidentate ligand, and MOL is a compound of formula (II) : (II) wherein X is C and R\ R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 and R12 are as defined herein. In another embodime
Soluble diamagnetic model for malaria pigment: Coordination chemistry of gallium(III)protoporphyrin-IX
Bohle, D. Scott,Dodd, Erin L.,Pinter, Tyler B. J.,Stillman, Martin J.
, p. 10747 - 10761 (2013/01/15)
The facile axial ligand exchange properties of gallium(III) protoporphyrin IX in methanol solution were utilized to explore self-association interactions by NMR techniques. Structural changes were observed, as well as competitive behavior with the ligands acetate and fluoride, which differed from that seen with the synthetic analogue gallium(III) octaethylporphyrin which lacks acid groups in its side-chains and has less solution heterogeneity as indicated by absorption and MCD spectroscopies. The propionic acid side chains of protoporphyrin IX are implicated in all such interactions of PPIX, and both dynamic metal-propionic interactions and the formation of propionate-bridged dimers are observed. Fluoride coordination provides an unusual example of slow ligand exchange, and this allows for the identification of a fluoride bridged dimer in solution. An improved synthesis of the chloride and hydroxide complexes of gallium(III) protoporphyrin IX is reported. An insoluble gallium analogue of hematin anhydride is described. In general, the interactions between solvent and the metal are found to confer very high solubility, making [Ga(PPIX)] + a useful model for ferric heme species.
Gallium(III) and indium(III) octaethylporphyrin dimeric complexes with a single μ-hydroxo bridge: Synthesis, structure and stability in anion-containing organic media
Parzuchowski, Pawe? G.,Kampf, Jeff W.,Ro?niecka, Ewa,Kondratenko, Yevgeniy,Malinowska, Elzbieta,Meyerhoff, Mark E.
, p. 302 - 313 (2008/10/09)
The synthesis and single-crystal X-ray structures of the hydroxo-bridged complexes (μ-hydroxo)-bis(octaethylporphinato)gallium(III)perchlorate {[Ga(OEP)]2OH}ClO4 and (μ-hydroxo)- bis(octaethylporphinato)indium(III)tetrakis[3,5-bis-(trifluoromethyl)phenyl] borate {[In(OEP)]2OH}TFPB are reported. These complexes are prepared by the titration of monomeric metalloporphyrin species in dichloromethane with diluted perchloric acid or by the addition of stoichiometric amounts of the tetraphenylborate derivative salt. The structures show that complexes of two metalloporphyrins are joined by a single protonated metal-oxygen-metal bridge with a nearly 150° bridge angle. The porphyrin rings of the dimers form dihedral angles of 15° Ga(III) and 23° In(III). In contrast to previously reported analogous dimeric Mn(III) and Fe(III) structures, the porphyrin rings of the present dimers are twisted by a much greater torsion angle of nearly 22°. In dichloromethane, high stability of the dimers is observed in the presence of perchlorate, but dissociation of the dimer species to monomers is found with increasing concentrations of halogen anions. This corresponds well with the observed anion selectivities recently reported for both electrochemical and optical anion sensors prepared with the respective Ga(III) and In(III) octaethylporphyrins in polymeric films.
Synthesis, electrochemistry, and ligand-addition reactions of gallium(III) porphyrins
Kadish,Cornillon,Coutsolelos,Guilard
, p. 4167 - 4173 (2008/10/08)
The synthesis, electrochemistry, and ligand-addition reactions of ionic five- and six-coordinate gallium(III) porphyrins are reported. The reactions of N-methylimidazole and pyridine with (P)GaX, where P = the dianion of octaethylporphyrin (OEP) or tetrap
SYNTHESE ET CARACTERISTIQUES PHYSICOCHIMIQUES DE GALLIOPORPHYRINES A LIAISON ? METAL-CARBONE
Coutsolelos, A.,Guilard, R.
, p. 273 - 282 (2007/10/02)
Novel gallium(III) porphyrins containing a metal-carbon bond have been prepared by the reaction of chlorogallium(III) porphyrins with organolithium derivatives of Grignard reagents.The products obtained are characterized on the basis of mass spectrometry, and 1H NMR and UV spectra.
