Exceptionally Facile CO Addition to a Saturated Ruthenium Complex
Synthesis and characterization of Cp*Ru[η3-HC(PPh2NPh)2], 1, reveals it to have a “piano stool” structure with the ligand bound to Ru(II) via two N and the unique, sp3 hybridized carbon. While the analogous (cymene) Ru[η3-HC(PPh2NPh)2]+ does not react with CO, under the same conditions, 1 adds one C...
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| Veröffentlicht in: | Journal of the American Chemical Society 2005-06, Vol.127 (25), p.8944-8945 |
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| container_title | Journal of the American Chemical Society |
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| creator | Bibal, Christine Smurnyy, Yegor D Pink, Maren Caulton, Kenneth G |
| description | Synthesis and characterization of Cp*Ru[η3-HC(PPh2NPh)2], 1, reveals it to have a “piano stool” structure with the ligand bound to Ru(II) via two N and the unique, sp3 hybridized carbon. While the analogous (cymene) Ru[η3-HC(PPh2NPh)2]+ does not react with CO, under the same conditions, 1 adds one CO rapidly (25 °C, 1 atm CO). Characterization, including an X-ray structure determination, shows that CO has displaced one chelate ligand nitrogen, which then hangs off the molecule, free of Ru. DFT calculations reveal a possible mechanism via a remarkably low energy (+9.3 kcal/mol) intermediate, pendant N, but with one phenyl on phosphorus stabilizing Ru via donation from a C(ipso)C(ortho) bond. DFT calculations show that the electronic energy change for binding CO is over 20 kcal/mol less favorable for cymene than for C5Me5 - as ligand; the reactivity difference is thus thermodynamic in origin. |
| doi_str_mv | 10.1021/ja051296h |
| format | Article |
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DFT calculations show that the electronic energy change for binding CO is over 20 kcal/mol less favorable for cymene than for C5Me5 - as ligand; the reactivity difference is thus thermodynamic in origin.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja051296h</identifier><identifier>PMID: 15969559</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Carbon Monoxide - chemistry ; Crystallography, X-Ray ; Models, Molecular ; Molecular Conformation ; Organometallic Compounds - chemical synthesis ; Organometallic Compounds - chemistry ; Ruthenium - chemistry ; Ruthenium Compounds - chemical synthesis ; Ruthenium Compounds - chemistry</subject><ispartof>Journal of the American Chemical Society, 2005-06, Vol.127 (25), p.8944-8945</ispartof><rights>Copyright © 2005 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a351t-11917ebd2e9b8b747a59214dd635be607e1ce965a15415ddc6e194a854fa7a7d3</citedby><cites>FETCH-LOGICAL-a351t-11917ebd2e9b8b747a59214dd635be607e1ce965a15415ddc6e194a854fa7a7d3</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/ja051296h$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja051296h$$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/15969559$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Bibal, Christine</creatorcontrib><creatorcontrib>Smurnyy, Yegor D</creatorcontrib><creatorcontrib>Pink, Maren</creatorcontrib><creatorcontrib>Caulton, Kenneth G</creatorcontrib><title>Exceptionally Facile CO Addition to a Saturated Ruthenium Complex</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>Synthesis and characterization of Cp*Ru[η3-HC(PPh2NPh)2], 1, reveals it to have a “piano stool” structure with the ligand bound to Ru(II) via two N and the unique, sp3 hybridized carbon. While the analogous (cymene) Ru[η3-HC(PPh2NPh)2]+ does not react with CO, under the same conditions, 1 adds one CO rapidly (25 °C, 1 atm CO). Characterization, including an X-ray structure determination, shows that CO has displaced one chelate ligand nitrogen, which then hangs off the molecule, free of Ru. DFT calculations reveal a possible mechanism via a remarkably low energy (+9.3 kcal/mol) intermediate, pendant N, but with one phenyl on phosphorus stabilizing Ru via donation from a C(ipso)C(ortho) bond. DFT calculations show that the electronic energy change for binding CO is over 20 kcal/mol less favorable for cymene than for C5Me5 - as ligand; the reactivity difference is thus thermodynamic in origin.</description><subject>Carbon Monoxide - chemistry</subject><subject>Crystallography, X-Ray</subject><subject>Models, Molecular</subject><subject>Molecular Conformation</subject><subject>Organometallic Compounds - chemical synthesis</subject><subject>Organometallic Compounds - chemistry</subject><subject>Ruthenium - chemistry</subject><subject>Ruthenium Compounds - chemical synthesis</subject><subject>Ruthenium Compounds - chemistry</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2005</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkE1PwkAQhjdGI_hx8A-YXjTxUN1pu7vskRDwiwQEvHjZTLtDKLYUu20C_94SCF48Td6ZJ-8kD2M3wB-BB_C0RC4g0HJxwtogAu43SZ6yNuc88FVHhi124dyyiVHQgXPWAqGlFkK3Wbe_SWhdpcUKs2zrDTBJM_J6I69rbbpbe1XhoTfFqi6xIutN6mpBq7TOvV6RrzPaXLGzOWaOrg_zkn0O-rPeiz8cPb_2ukMfQwGVD6BBUWwD0nEnVpFCoQOIrJWhiElyRZCQlgJBRCCsTSSBjrAjojkqVDa8ZPf73nVZ_NTkKpOnLqEswxUVtTNSaaEUqAZ82INJWThX0tysyzTHcmuAm50vc_TVsLeH0jrOyf6RB0EN4O-B1FW0Od6x_G4ehkqY2Xhqvj7exu9aToxo-Ls9j4kzy6IuG6_un8e_5ZB_ow</recordid><startdate>20050629</startdate><enddate>20050629</enddate><creator>Bibal, Christine</creator><creator>Smurnyy, Yegor D</creator><creator>Pink, Maren</creator><creator>Caulton, Kenneth G</creator><general>American Chemical Society</general><scope>BSCLL</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></search><sort><creationdate>20050629</creationdate><title>Exceptionally Facile CO Addition to a Saturated Ruthenium Complex</title><author>Bibal, Christine ; Smurnyy, Yegor D ; Pink, Maren ; Caulton, Kenneth G</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a351t-11917ebd2e9b8b747a59214dd635be607e1ce965a15415ddc6e194a854fa7a7d3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2005</creationdate><topic>Carbon Monoxide - chemistry</topic><topic>Crystallography, X-Ray</topic><topic>Models, Molecular</topic><topic>Molecular Conformation</topic><topic>Organometallic Compounds - chemical synthesis</topic><topic>Organometallic Compounds - chemistry</topic><topic>Ruthenium - chemistry</topic><topic>Ruthenium Compounds - chemical synthesis</topic><topic>Ruthenium Compounds - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Bibal, Christine</creatorcontrib><creatorcontrib>Smurnyy, Yegor D</creatorcontrib><creatorcontrib>Pink, Maren</creatorcontrib><creatorcontrib>Caulton, Kenneth G</creatorcontrib><collection>Istex</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><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Bibal, Christine</au><au>Smurnyy, Yegor D</au><au>Pink, Maren</au><au>Caulton, Kenneth G</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Exceptionally Facile CO Addition to a Saturated Ruthenium Complex</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2005-06-29</date><risdate>2005</risdate><volume>127</volume><issue>25</issue><spage>8944</spage><epage>8945</epage><pages>8944-8945</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>Synthesis and characterization of Cp*Ru[η3-HC(PPh2NPh)2], 1, reveals it to have a “piano stool” structure with the ligand bound to Ru(II) via two N and the unique, sp3 hybridized carbon. While the analogous (cymene) Ru[η3-HC(PPh2NPh)2]+ does not react with CO, under the same conditions, 1 adds one CO rapidly (25 °C, 1 atm CO). Characterization, including an X-ray structure determination, shows that CO has displaced one chelate ligand nitrogen, which then hangs off the molecule, free of Ru. DFT calculations reveal a possible mechanism via a remarkably low energy (+9.3 kcal/mol) intermediate, pendant N, but with one phenyl on phosphorus stabilizing Ru via donation from a C(ipso)C(ortho) bond. DFT calculations show that the electronic energy change for binding CO is over 20 kcal/mol less favorable for cymene than for C5Me5 - as ligand; the reactivity difference is thus thermodynamic in origin.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>15969559</pmid><doi>10.1021/ja051296h</doi><tpages>2</tpages></addata></record> |
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| source | ACS Publications; MEDLINE |
| subjects | Carbon Monoxide - chemistry Crystallography, X-Ray Models, Molecular Molecular Conformation Organometallic Compounds - chemical synthesis Organometallic Compounds - chemistry Ruthenium - chemistry Ruthenium Compounds - chemical synthesis Ruthenium Compounds - chemistry |
| title | Exceptionally Facile CO Addition to a Saturated Ruthenium Complex |
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