Gallium(III) Tetraphenylporphyrinates Containing Hydrosulfide and Thiolate Ligands: Structural Models for Sulfur-Bound Iron(III) Hemes
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...
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| Veröffentlicht in: | Inorganic chemistry 2016-03, Vol.55 (5), p.2421-2426 |
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| container_title | Inorganic chemistry |
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| creator | Meininger, Daniel J Chee-Garza, Max Arman, Hadi D Tonzetich, Zachary J |
| description | 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. |
| doi_str_mv | 10.1021/acs.inorgchem.5b02822 |
| format | Article |
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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.</description><identifier>ISSN: 0020-1669</identifier><identifier>EISSN: 1520-510X</identifier><identifier>DOI: 10.1021/acs.inorgchem.5b02822</identifier><identifier>PMID: 26872092</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Crystallography, X-Ray ; Ferric Compounds - chemistry ; Gallium - chemistry ; Heme - chemistry ; Hydrogen Sulfide - chemistry ; Ligands ; Models, Molecular ; Porphyrins - chemistry ; Sulfhydryl Compounds - chemistry ; Sulfur - chemistry</subject><ispartof>Inorganic chemistry, 2016-03, Vol.55 (5), p.2421-2426</ispartof><rights>Copyright © 2016 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a351t-442553c4442354bcaa285b4c212a833731ed22a9d534acfe762b4f236bdef7ed3</citedby><cites>FETCH-LOGICAL-a351t-442553c4442354bcaa285b4c212a833731ed22a9d534acfe762b4f236bdef7ed3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.5b02822$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5b02822$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2752,27053,27901,27902,56713,56763</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/26872092$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Meininger, Daniel J</creatorcontrib><creatorcontrib>Chee-Garza, Max</creatorcontrib><creatorcontrib>Arman, Hadi D</creatorcontrib><creatorcontrib>Tonzetich, Zachary J</creatorcontrib><title>Gallium(III) Tetraphenylporphyrinates Containing Hydrosulfide and Thiolate Ligands: Structural Models for Sulfur-Bound Iron(III) Hemes</title><title>Inorganic chemistry</title><addtitle>Inorg. Chem</addtitle><description>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.</description><subject>Crystallography, X-Ray</subject><subject>Ferric Compounds - chemistry</subject><subject>Gallium - chemistry</subject><subject>Heme - chemistry</subject><subject>Hydrogen Sulfide - chemistry</subject><subject>Ligands</subject><subject>Models, Molecular</subject><subject>Porphyrins - chemistry</subject><subject>Sulfhydryl Compounds - chemistry</subject><subject>Sulfur - chemistry</subject><issn>0020-1669</issn><issn>1520-510X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2016</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqFkb9u2zAQh4miQeOmfYQWHNNBLv9KcrfGaGMBDjLEBboJlHiyGVCkSoqDX6DPHQZ2smY6Evi-O9z9EPpCyZISRr-rPi6N82HfH2Bcyo6wmrF3aEElI4Wk5O97tCAkv2lZri7RxxgfCSErLsoP6JKVdcXIii3Q_1tlrUnjddM03_AO5qCmA7ijnXyYDsdgnJoh4rV3szLOuD3eHHXwMdnBaMDKabw7GG8zhbdmn__xB36YQ-rnFJTFd16DjXjwAT9kJ4XixqcsNcG708wNjBA_oYtB2Qifz_UK_fn9a7feFNv722b9c1soLulcCMGk5L3IlUvR9UqxWnaiZ5SpmvOKU9CMqZWWXKh-gKpknRgYLzsNQwWaX6HrU98p-H8J4tyOJvZgrXLgU2xpVVEhalGKjMoT2ud1Y4ChnYIZVTi2lLTPEbQ5gvY1gvYcQfa-nkekbgT9ar3cPAP0BDz7jz4Flzd-o-kTtuaYqw</recordid><startdate>20160307</startdate><enddate>20160307</enddate><creator>Meininger, Daniel J</creator><creator>Chee-Garza, Max</creator><creator>Arman, Hadi D</creator><creator>Tonzetich, Zachary J</creator><general>American Chemical Society</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20160307</creationdate><title>Gallium(III) Tetraphenylporphyrinates Containing Hydrosulfide and Thiolate Ligands: Structural Models for Sulfur-Bound Iron(III) Hemes</title><author>Meininger, Daniel J ; Chee-Garza, Max ; Arman, Hadi D ; Tonzetich, Zachary J</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a351t-442553c4442354bcaa285b4c212a833731ed22a9d534acfe762b4f236bdef7ed3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2016</creationdate><topic>Crystallography, X-Ray</topic><topic>Ferric Compounds - chemistry</topic><topic>Gallium - chemistry</topic><topic>Heme - chemistry</topic><topic>Hydrogen Sulfide - chemistry</topic><topic>Ligands</topic><topic>Models, Molecular</topic><topic>Porphyrins - chemistry</topic><topic>Sulfhydryl Compounds - chemistry</topic><topic>Sulfur - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Meininger, Daniel J</creatorcontrib><creatorcontrib>Chee-Garza, Max</creatorcontrib><creatorcontrib>Arman, Hadi D</creatorcontrib><creatorcontrib>Tonzetich, Zachary J</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Meininger, Daniel J</au><au>Chee-Garza, Max</au><au>Arman, Hadi D</au><au>Tonzetich, Zachary J</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Gallium(III) Tetraphenylporphyrinates Containing Hydrosulfide and Thiolate Ligands: Structural Models for Sulfur-Bound Iron(III) Hemes</atitle><jtitle>Inorganic chemistry</jtitle><addtitle>Inorg. Chem</addtitle><date>2016-03-07</date><risdate>2016</risdate><volume>55</volume><issue>5</issue><spage>2421</spage><epage>2426</epage><pages>2421-2426</pages><issn>0020-1669</issn><eissn>1520-510X</eissn><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.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>26872092</pmid><doi>10.1021/acs.inorgchem.5b02822</doi><tpages>6</tpages></addata></record> |
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| source | ACS Publications; MEDLINE |
| subjects | Crystallography, X-Ray Ferric Compounds - chemistry Gallium - chemistry Heme - chemistry Hydrogen Sulfide - chemistry Ligands Models, Molecular Porphyrins - chemistry Sulfhydryl Compounds - chemistry Sulfur - chemistry |
| title | Gallium(III) Tetraphenylporphyrinates Containing Hydrosulfide and Thiolate Ligands: Structural Models for Sulfur-Bound Iron(III) Hemes |
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