title: Gallium(III) Tetraphenylporphyrinates Containing Hydrosulfide and Thiolate Ligands: Structural Models for Sulfur-Bound Iron(III) Hemes.
abstract: Gallium(III) tetraphenylporphyrinates (TPP) containing anionic sulfur ligands have been prepared and characterized in the solid state and solution. The complexes serve as structural models for iron(III) heme sites containing sulfur coordination that otherwise prove challenging to synthesize due to the propensity for reduction to iron(II). The compounds prepared include the first well-characterized example of a trivalent metalloporphyrinate containing a terminal hydrosulfide ligand, [Ga(SH)(TPP)], as well as [Ga(SEt)(TPP)], [Ga(SPh)(TPP)], and [Ga(SSi(i)Pr3)(TPP)]. The stability of these compounds toward reduction has permitted an investigation of their solid-state structures and electrochemistry. The structural features and reaction chemistry of the complexes in relation to their iron(III) analogs is discussed.
authors.affiliation: Department of Chemistry, University of Texas at San Antonio (UTSA) , San Antonio Texas 78249, United States.
authors.forename: Daniel J
authors.initials: DJ
authors.lastname: Meininger
authors.affiliation: Department of Chemistry, University of Texas at San Antonio (UTSA) , San Antonio Texas 78249, United States.
authors.forename: Max
authors.initials: M
authors.lastname: Chee-Garza
authors.affiliation: Department of Chemistry, University of Texas at San Antonio (UTSA) , San Antonio Texas 78249, United States.
authors.forename: Hadi D
authors.initials: HD
authors.lastname: Arman
authors.affiliation: Department of Chemistry, University of Texas at San Antonio (UTSA) , San Antonio Texas 78249, United States.
authors.forename: Zachary J
authors.initials: ZJ
authors.lastname: Tonzetich
mesh_terms: D018360:Crystallography, X-Ray; D005290:Ferric Compounds / Q000737:chemistry*; D005708:Gallium / Q000737:chemistry*; D006418:Heme / Q000737:chemistry*; D006862:Hydrogen Sulfide / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D011166:Porphyrins / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*
chemical_list: D005290:Ferric Compounds; D008024:Ligands; D011166:Porphyrins; D013438:Sulfhydryl Compounds; D006418:Heme; D013455:Sulfur; D005708:Gallium; D006862:Hydrogen Sulfide