Halide-Dependent Mechanisms of Reductive Elimination from Gold(III)
Two unique organometallic halide series (Ph3P)Au(4-Me-C6H4)(CF3)(X) and (Cy3P)Au(4-F-C6H4)(CF3)(X) (X = I, Br, Cl, F) have been synthesized. The PPh3-supported complexes can undergo both Caryl–X and Caryl–CF3 reductive elimination. Mechanistic studies of thermolysis at 122 °C reveal a dramat...
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| Veröffentlicht in: | Journal of the American Chemical Society 2015-06, Vol.137 (24), p.7921-7928 |
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| container_title | Journal of the American Chemical Society |
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| creator | Winston, Matthew S Wolf, William J Toste, F. Dean |
| description | Two unique organometallic halide series (Ph3P)Au(4-Me-C6H4)(CF3)(X) and (Cy3P)Au(4-F-C6H4)(CF3)(X) (X = I, Br, Cl, F) have been synthesized. The PPh3-supported complexes can undergo both Caryl–X and Caryl–CF3 reductive elimination. Mechanistic studies of thermolysis at 122 °C reveal a dramatic reactivity and kinetic selectivity dependence on halide ligand. For X = I or F, zero-order kinetic behavior is observed, while for X = Cl or Br, kinetic studies implicate product catalysis. The selectivity for Caryl–CF3 bond formation increases in the order X = I < Br < Cl < F, with exclusively Caryl–I bond formation when X = I, and exclusively Caryl–CF3 bond formation when X = F. Thermodynamic measurements show that Au(III)–X bond dissociation energies increase in the order X = I < Br < Cl, and that ground state Au(III)–X bond strength ultimately dictates selectivities for Caryl–X and Caryl–CF3 reductive elimination. |
| doi_str_mv | 10.1021/jacs.5b04613 |
| format | Article |
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Dean</creatorcontrib><title>Halide-Dependent Mechanisms of Reductive Elimination from Gold(III)</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>Two unique organometallic halide series (Ph3P)Au(4-Me-C6H4)(CF3)(X) and (Cy3P)Au(4-F-C6H4)(CF3)(X) (X = I, Br, Cl, F) have been synthesized. The PPh3-supported complexes can undergo both Caryl–X and Caryl–CF3 reductive elimination. Mechanistic studies of thermolysis at 122 °C reveal a dramatic reactivity and kinetic selectivity dependence on halide ligand. For X = I or F, zero-order kinetic behavior is observed, while for X = Cl or Br, kinetic studies implicate product catalysis. The selectivity for Caryl–CF3 bond formation increases in the order X = I < Br < Cl < F, with exclusively Caryl–I bond formation when X = I, and exclusively Caryl–CF3 bond formation when X = F. Thermodynamic measurements show that Au(III)–X bond dissociation energies increase in the order X = I < Br < Cl, and that ground state Au(III)–X bond strength ultimately dictates selectivities for Caryl–X and Caryl–CF3 reductive elimination.</description><subject>Bonding</subject><subject>Bonding strength</subject><subject>Bromides - chemistry</subject><subject>bromine</subject><subject>catalytic activity</subject><subject>Chlorides - chemistry</subject><subject>dissociation</subject><subject>Fluorides - chemistry</subject><subject>Free energy</subject><subject>gold</subject><subject>Halides</subject><subject>Halogens - chemistry</subject><subject>Heat of formation</subject><subject>Hot Temperature</subject><subject>Iodides - chemistry</subject><subject>iodine</subject><subject>Ligands</subject><subject>Models, Molecular</subject><subject>Organogold Compounds - chemistry</subject><subject>Oxidation-Reduction</subject><subject>Reaction kinetics</subject><subject>Selectivity</subject><subject>thermal degradation</subject><subject>Thermodynamics</subject><issn>0002-7863</issn><issn>1520-5126</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><sourceid>N~.</sourceid><sourceid>EIF</sourceid><recordid>eNqFkctr3DAQxkVJaDZpbz0HH1OoE83ofQmUbR4LCYHSnoUsy40W29pYdqD_fb1kmzYQyGkY5jffPD5CPgE9BYpwtnY-n4qKcgnsHVmAQFoKQLlHFpRSLJWW7IAc5ryeU44a3pMDlFQKhbggy2vXxjqU38Im9HXox-I2-HvXx9zlIjXF91BPfoyPobhoYxd7N8bUF82QuuIqtfXJarX6_IHsN67N4eMuHpGflxc_ltflzd3Vavn1pnRcs7FkqAxHEVAH5xunDVS0qqVgFDQo0zSuopIHD5qpynhNqRFKUy0Mal9rw47I-ZPuZqq6UPt528G1djPEzg2_bXLRvqz08d7-So-Wc40cxCxwshMY0sMU8mi7mH1oW9eHNGWLnIEWiqF8EwWNQgBlhr2NSgNouAI1o1-eUD-knIfQPC8P1G7dtFs37c7NGT_-_-Bn-K99_0Zvu9ZpGvr5_69r_QGmfKYv</recordid><startdate>20150624</startdate><enddate>20150624</enddate><creator>Winston, Matthew S</creator><creator>Wolf, William J</creator><creator>Toste, F. Dean</creator><general>American Chemical Society</general><scope>N~.</scope><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><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>7S9</scope><scope>L.6</scope><scope>5PM</scope></search><sort><creationdate>20150624</creationdate><title>Halide-Dependent Mechanisms of Reductive Elimination from Gold(III)</title><author>Winston, Matthew S ; Wolf, William J ; Toste, F. Dean</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a483t-3279425e28eacfa891b0bd653018179ffab064ec1837b9c8009578085928cd893</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>Bonding</topic><topic>Bonding strength</topic><topic>Bromides - chemistry</topic><topic>bromine</topic><topic>catalytic activity</topic><topic>Chlorides - chemistry</topic><topic>dissociation</topic><topic>Fluorides - chemistry</topic><topic>Free energy</topic><topic>gold</topic><topic>Halides</topic><topic>Halogens - chemistry</topic><topic>Heat of formation</topic><topic>Hot Temperature</topic><topic>Iodides - chemistry</topic><topic>iodine</topic><topic>Ligands</topic><topic>Models, Molecular</topic><topic>Organogold Compounds - chemistry</topic><topic>Oxidation-Reduction</topic><topic>Reaction kinetics</topic><topic>Selectivity</topic><topic>thermal degradation</topic><topic>Thermodynamics</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Winston, Matthew S</creatorcontrib><creatorcontrib>Wolf, William J</creatorcontrib><creatorcontrib>Toste, F. Dean</creatorcontrib><collection>American Chemical Society (ACS) Open Access</collection><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><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>AGRICOLA</collection><collection>AGRICOLA - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Winston, Matthew S</au><au>Wolf, William J</au><au>Toste, F. Dean</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Halide-Dependent Mechanisms of Reductive Elimination from Gold(III)</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2015-06-24</date><risdate>2015</risdate><volume>137</volume><issue>24</issue><spage>7921</spage><epage>7928</epage><pages>7921-7928</pages><issn>0002-7863</issn><issn>1520-5126</issn><eissn>1520-5126</eissn><abstract>Two unique organometallic halide series (Ph3P)Au(4-Me-C6H4)(CF3)(X) and (Cy3P)Au(4-F-C6H4)(CF3)(X) (X = I, Br, Cl, F) have been synthesized. The PPh3-supported complexes can undergo both Caryl–X and Caryl–CF3 reductive elimination. Mechanistic studies of thermolysis at 122 °C reveal a dramatic reactivity and kinetic selectivity dependence on halide ligand. For X = I or F, zero-order kinetic behavior is observed, while for X = Cl or Br, kinetic studies implicate product catalysis. The selectivity for Caryl–CF3 bond formation increases in the order X = I < Br < Cl < F, with exclusively Caryl–I bond formation when X = I, and exclusively Caryl–CF3 bond formation when X = F. Thermodynamic measurements show that Au(III)–X bond dissociation energies increase in the order X = I < Br < Cl, and that ground state Au(III)–X bond strength ultimately dictates selectivities for Caryl–X and Caryl–CF3 reductive elimination.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>26065722</pmid><doi>10.1021/jacs.5b04613</doi><tpages>8</tpages><oa>free_for_read</oa></addata></record> |
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| subjects | Bonding Bonding strength Bromides - chemistry bromine catalytic activity Chlorides - chemistry dissociation Fluorides - chemistry Free energy gold Halides Halogens - chemistry Heat of formation Hot Temperature Iodides - chemistry iodine Ligands Models, Molecular Organogold Compounds - chemistry Oxidation-Reduction Reaction kinetics Selectivity thermal degradation Thermodynamics |
| title | Halide-Dependent Mechanisms of Reductive Elimination from Gold(III) |
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