Synthesis, electrochemistry, and ligand-addition reactions of gallium(III) porphyrins

Soluble Diamagnetic Model for Malaria Pigment: Coordination Chemistry of Gallium(III)protoporphyrin-IX

“…1 Spectroscopically identical to literature report. 13 Preparation of Ga(OEP)(OMe) (6). Gallium(III) octaethylporphyrin chloride (500 mg) was dissolved in methanol (100 mL) and left sitting for 24 h. Solvent was removed in vacuo at 60°C, and the solid residue left under vacuum overnight.…”

“…Spectroscopically identical to literature report. 13 Methods. NMR Titration of Ga(PPIX)(X) (X = Cl, OH) against Ligand Source (Acetic Acid) or Base (Tetramethylammonium Hydroxide).…”

Building from Ga‐Porphyrins: Synthesis of Ga‐Acetylide Complexes Using Acetylenes and Polyynes

“…Thus,e ven though the aryl groups are orientated orthogonal to the plane of the TTBP porphyrin owing to steric congestion, [27] fast rotation on the NMR time scale ensures degeneracyo ft he protons. [28] Ford erivatives of TPFP (2b-13 b), however,r ing rotation is slower,a nd individual resonances of all five fluorine atoms are apparent in the 19 FNMR spectra with the expected F-F coupling.I mportantly,i nequivalence of the aryl fluorine atoms in the 19 FNMR spectra also confirms the absence of ligand exchange of the axial acetylides in the dyads. [16] 1 HNMR spectra of porphyrin acetylide complexes show the influence of diamagnetic anisotropy,t ypical for porphyrinoids.Namely, 1 Hresonances from the axial acetylide ligands are shifted upfield, and the magnitude of the shift can be nicely correlated as afunction of distance from the porphyrin core,a si nt he series of triisopropylsilylacetylides derivatives 4b/9b/12 b (Figure 2) and phenylacetylides 3b/8b/11 b (Figure S20 in the Supporting Information).…”

“…Insertion of the Ga III cation into the porphyrin core was accomplished by adaptation of aliterature protocol, based on the use of GaCl 3 in boiling acetic acid. [19,20] Thea cidic medium, however, could be replaced by benzonitrile,w hich offered easier workup and insertion yields of about 80 %(see the Supporting Information for details). Substitution of the axial chlorine anion with an acetylide was achieved by treatment of 1a with af reshly prepared Grignard reagent or lithium acetylide (see Table 1and the Supporting Information for details), [15,16] using an excess of the acetylide (2-5 equiv).…”

Responses of Metalloporphyrin‐Based Ion‐Selective Electrodes to pH

“…As described in the text, this complex was transformed into [Al(tpp)(OH)] according to the total concentration of the complex and water in organic solvents. The gallium-and indium-chloro complexes were prepared as described in literature [33,34], and were similarly converted to [Ga (tpp) [3,5-bis(trifluoromethyl)phenyl]borate (NaTFPB, Wako), sodium dodecyl sulfate (NaDS, Wako), and sodium perfluorooctanesulfonate (NaPFOS, Wako), were used as received. As a membrane solvent, 2-nitrophenyl octyl ether (o-NPOE) was prepared by modifying the method in the literature, while dioctyl sebacate (DOS) was used as received.…”