Isolation of an Elusive Phosphametallacyclobutadiene and Its Role in Reversible Carbon−Carbon Bond Cleavage
The reactivity of phosphaalkynes, the isolobal and isoelectronic congeners to alkynes, with metal alkylidyne complexes is explored in this work. Treating the tungsten alkylidyne [tBuOCO]W≡CtBu(THF)2 (1) with phosphaalkyne (10) results in the formation of [O2C(tBuC=)W{η2‐(P,C)−P≡C−Ad}(THF)] (13‐tBuTH...
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creator | Jakhar, Vineet K. Esper, Alec M. Ghiviriga, Ion Abboud, Khalil A. Ehm, Christian Veige, Adam S. |
description | The reactivity of phosphaalkynes, the isolobal and isoelectronic congeners to alkynes, with metal alkylidyne complexes is explored in this work. Treating the tungsten alkylidyne [tBuOCO]W≡CtBu(THF)2 (1) with phosphaalkyne (10) results in the formation of [O2C(tBuC=)W{η2‐(P,C)−P≡C−Ad}(THF)] (13‐tBuTHF) and [O2C(AdC=)W{η2‐(P,C)−P≡C−tBu}(THF)] (13‐AdTHF); derived from the formal reductive migratory insertion of the alkylidyne moiety into a W−Carene bond. Analogous to alkyne metathesis, a stable phosphametallacyclobutadiene complex [tBuOCO]W[κ2‐C(tBu)PC(Ad)] (14) forms upon loss of THF from the coordination sphere of either 13‐tBuTHF or 13‐AdTHF. Remarkably, the C−C bonds reversibly form/cleave with the addition or removal of THF from the coordination sphere of the formal tungsten(VI) metal center, permitting unprecedented control over the transformation of a tetraanionic pincer to a trianionic pincer and back. Computational analysis offers thermodynamic and electronic reasoning for the reversible equilibrium between 13‐tBu/AdTHF and 14.
The elusive phosphametallacyclobutadiene intermediate is isolated and characterized. This intermediate reveals insights into rapid and reversible C−C bond formation/cleavage, enabling the cycling between a trianionic pincer and a tetraanionic pincer ligand at will. |
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The elusive phosphametallacyclobutadiene intermediate is isolated and characterized. This intermediate reveals insights into rapid and reversible C−C bond formation/cleavage, enabling the cycling between a trianionic pincer and a tetraanionic pincer ligand at will.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202203073</identifier><identifier>PMID: 35536109</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Alkylidynes ; Alkynes ; Carbon ; Computer applications ; Congeners ; Coordination ; Cycloaddition ; C−C Activation ; Metallacycles ; Metathesis ; Phosphaalkynes ; Tungsten</subject><ispartof>Angewandte Chemie International Edition, 2022-07, Vol.61 (30), p.e202203073-n/a</ispartof><rights>2022 Wiley‐VCH GmbH</rights><rights>2022 Wiley-VCH GmbH.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4683-33275ce28d54096308691ca588469e4fad857e64a81cd223d955789da49948253</citedby><cites>FETCH-LOGICAL-c4683-33275ce28d54096308691ca588469e4fad857e64a81cd223d955789da49948253</cites><orcidid>0000-0002-7020-9251</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fanie.202203073$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.202203073$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>230,314,776,780,881,1411,27901,27902,45550,45551</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/35536109$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Jakhar, Vineet K.</creatorcontrib><creatorcontrib>Esper, Alec M.</creatorcontrib><creatorcontrib>Ghiviriga, Ion</creatorcontrib><creatorcontrib>Abboud, Khalil A.</creatorcontrib><creatorcontrib>Ehm, Christian</creatorcontrib><creatorcontrib>Veige, Adam S.</creatorcontrib><title>Isolation of an Elusive Phosphametallacyclobutadiene and Its Role in Reversible Carbon−Carbon Bond Cleavage</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>The reactivity of phosphaalkynes, the isolobal and isoelectronic congeners to alkynes, with metal alkylidyne complexes is explored in this work. Treating the tungsten alkylidyne [tBuOCO]W≡CtBu(THF)2 (1) with phosphaalkyne (10) results in the formation of [O2C(tBuC=)W{η2‐(P,C)−P≡C−Ad}(THF)] (13‐tBuTHF) and [O2C(AdC=)W{η2‐(P,C)−P≡C−tBu}(THF)] (13‐AdTHF); derived from the formal reductive migratory insertion of the alkylidyne moiety into a W−Carene bond. Analogous to alkyne metathesis, a stable phosphametallacyclobutadiene complex [tBuOCO]W[κ2‐C(tBu)PC(Ad)] (14) forms upon loss of THF from the coordination sphere of either 13‐tBuTHF or 13‐AdTHF. Remarkably, the C−C bonds reversibly form/cleave with the addition or removal of THF from the coordination sphere of the formal tungsten(VI) metal center, permitting unprecedented control over the transformation of a tetraanionic pincer to a trianionic pincer and back. Computational analysis offers thermodynamic and electronic reasoning for the reversible equilibrium between 13‐tBu/AdTHF and 14.
The elusive phosphametallacyclobutadiene intermediate is isolated and characterized. This intermediate reveals insights into rapid and reversible C−C bond formation/cleavage, enabling the cycling between a trianionic pincer and a tetraanionic pincer ligand at will.</description><subject>Alkylidynes</subject><subject>Alkynes</subject><subject>Carbon</subject><subject>Computer applications</subject><subject>Congeners</subject><subject>Coordination</subject><subject>Cycloaddition</subject><subject>C−C Activation</subject><subject>Metallacycles</subject><subject>Metathesis</subject><subject>Phosphaalkynes</subject><subject>Tungsten</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><recordid>eNqFkctuEzEUhkcIREthyxJZYsNmgu9jb5BKlEKkClAFa8vxnDSuPHawZ4LyBqz7iDwJrlLCZcPKxzrf-c_lb5rnBM8IxvS1jR5mFFOKGe7Yg-aUCEpa1nXsYY05Y22nBDlpnpRyU3mlsHzcnDAhmCRYnzbDsqRgR58iSmtkI1qEqfgdoE-bVLYbO8BoQ7Bu70JaTaPtPUSoXI-WY0FXKQDyEV3BDnLxq_qb27xK8cf320OA3qbKzgPYnb2Gp82jtQ0Fnt2_Z82Xi8Xn-fv28uO75fz8snVcKtYyRjvhgKpecKwlw0pq4qxQiksNfG17JTqQ3CriekpZr4XolO4t15orKthZ8-agu51WA_QO4phtMNvsB5v3Jllv_s5EvzHXaWc01VJwWQVe3Qvk9HWCMprBFwf1EhHSVAyVktSmddCKvvwHvUlTjnW9Smms68V1V6nZgXI5lZJhfRyGYHPnpLlz0hydrAUv_lzhiP-yrgL6AHzzAfb_kTPnH5aL3-I_AXtyq4g</recordid><startdate>20220725</startdate><enddate>20220725</enddate><creator>Jakhar, Vineet K.</creator><creator>Esper, Alec M.</creator><creator>Ghiviriga, Ion</creator><creator>Abboud, Khalil A.</creator><creator>Ehm, Christian</creator><creator>Veige, Adam S.</creator><general>Wiley Subscription Services, Inc</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0002-7020-9251</orcidid></search><sort><creationdate>20220725</creationdate><title>Isolation of an Elusive Phosphametallacyclobutadiene and Its Role in Reversible Carbon−Carbon Bond Cleavage</title><author>Jakhar, Vineet K. ; Esper, Alec M. ; Ghiviriga, Ion ; Abboud, Khalil A. ; Ehm, Christian ; Veige, Adam S.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4683-33275ce28d54096308691ca588469e4fad857e64a81cd223d955789da49948253</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><topic>Alkylidynes</topic><topic>Alkynes</topic><topic>Carbon</topic><topic>Computer applications</topic><topic>Congeners</topic><topic>Coordination</topic><topic>Cycloaddition</topic><topic>C−C Activation</topic><topic>Metallacycles</topic><topic>Metathesis</topic><topic>Phosphaalkynes</topic><topic>Tungsten</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Jakhar, Vineet K.</creatorcontrib><creatorcontrib>Esper, Alec M.</creatorcontrib><creatorcontrib>Ghiviriga, Ion</creatorcontrib><creatorcontrib>Abboud, Khalil A.</creatorcontrib><creatorcontrib>Ehm, Christian</creatorcontrib><creatorcontrib>Veige, Adam S.</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Jakhar, Vineet K.</au><au>Esper, Alec M.</au><au>Ghiviriga, Ion</au><au>Abboud, Khalil A.</au><au>Ehm, Christian</au><au>Veige, Adam S.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Isolation of an Elusive Phosphametallacyclobutadiene and Its Role in Reversible Carbon−Carbon Bond Cleavage</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2022-07-25</date><risdate>2022</risdate><volume>61</volume><issue>30</issue><spage>e202203073</spage><epage>n/a</epage><pages>e202203073-n/a</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>The reactivity of phosphaalkynes, the isolobal and isoelectronic congeners to alkynes, with metal alkylidyne complexes is explored in this work. Treating the tungsten alkylidyne [tBuOCO]W≡CtBu(THF)2 (1) with phosphaalkyne (10) results in the formation of [O2C(tBuC=)W{η2‐(P,C)−P≡C−Ad}(THF)] (13‐tBuTHF) and [O2C(AdC=)W{η2‐(P,C)−P≡C−tBu}(THF)] (13‐AdTHF); derived from the formal reductive migratory insertion of the alkylidyne moiety into a W−Carene bond. Analogous to alkyne metathesis, a stable phosphametallacyclobutadiene complex [tBuOCO]W[κ2‐C(tBu)PC(Ad)] (14) forms upon loss of THF from the coordination sphere of either 13‐tBuTHF or 13‐AdTHF. Remarkably, the C−C bonds reversibly form/cleave with the addition or removal of THF from the coordination sphere of the formal tungsten(VI) metal center, permitting unprecedented control over the transformation of a tetraanionic pincer to a trianionic pincer and back. Computational analysis offers thermodynamic and electronic reasoning for the reversible equilibrium between 13‐tBu/AdTHF and 14.
The elusive phosphametallacyclobutadiene intermediate is isolated and characterized. This intermediate reveals insights into rapid and reversible C−C bond formation/cleavage, enabling the cycling between a trianionic pincer and a tetraanionic pincer ligand at will.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>35536109</pmid><doi>10.1002/anie.202203073</doi><tpages>8</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0002-7020-9251</orcidid><oa>free_for_read</oa></addata></record> |
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subjects | Alkylidynes Alkynes Carbon Computer applications Congeners Coordination Cycloaddition C−C Activation Metallacycles Metathesis Phosphaalkynes Tungsten |
title | Isolation of an Elusive Phosphametallacyclobutadiene and Its Role in Reversible Carbon−Carbon Bond Cleavage |
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