Gallium(III) Tetraphenylporphyrinates Containing Hydrosulfide and Thiolate Ligands: Structural Models for Sulfur-Bound Iron(III) Hemes

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• 作者：Daniel J. Meininger ; Max Chee-Garza ; Hadi D. Arman ; Zachary J. Tonzetich
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：March 7, 2016
• 年：2016
• 卷：55
• 期：5
• 页码：2421-2426
• 全文大小：427K
• ISSN：1520-510X

文摘

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(SSiⁱPr₃)(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.