Phosphorus stabilized carbene complexes: bisphosphonate dianion synthesis, reactivity and DFT studies of O~C~O zirconium(IV) complexes
The reactivity of the geminal dianion of tetraisopropyl methylenediphosphonate, 3, with [ZrCl4(THF)2] affords a trinuclear structure 5 in which an unprecedented triscarbene-Zr dianionic fragment is found. The overall trinuclear arrangement is assembled by PO bridging moieties. The X-ray crystal stru...
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Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2010-01, Vol.39 (2), p.492-499 |
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creator | Heuclin, Hadrien Grünstein, Dan Le Goff, Xavier-Frederic Le Floch, Pascal Mézailles, Nicolas |
description | The reactivity of the geminal dianion of tetraisopropyl methylenediphosphonate, 3, with [ZrCl4(THF)2] affords a trinuclear structure 5 in which an unprecedented triscarbene-Zr dianionic fragment is found. The overall trinuclear arrangement is assembled by PO bridging moieties. The X-ray crystal structure of 5 is presented. The reaction of complex 5 with stoichiometric amounts of pyridine affords a dinuclear complex 6 whose formulation was ascertained by an X-ray crystal structure. Complexes 5 and 6 cleanly react with aldehydes (R1)(H)CO to afford the corresponding olefin of general formula [((OiPr)2P=O)2C=C(R1)(H)]. DFT calculations which were carried out on the model complex of 5t and a hypothetical monometallic Zr complex [Zr(3)Cl2(OMe2)2] 8t indicate that the Zr-C bond only features a weak pi-interaction between the carbon atom and a vacant orbital at the metal. The polarization of the orbital towards the carbon center is consistent with the observed nucleophilic character of the carbene complexes described here. |
doi_str_mv | 10.1039/b915468j |
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The overall trinuclear arrangement is assembled by PO bridging moieties. The X-ray crystal structure of 5 is presented. The reaction of complex 5 with stoichiometric amounts of pyridine affords a dinuclear complex 6 whose formulation was ascertained by an X-ray crystal structure. Complexes 5 and 6 cleanly react with aldehydes (R1)(H)CO to afford the corresponding olefin of general formula [((OiPr)2P=O)2C=C(R1)(H)]. DFT calculations which were carried out on the model complex of 5t and a hypothetical monometallic Zr complex [Zr(3)Cl2(OMe2)2] 8t indicate that the Zr-C bond only features a weak pi-interaction between the carbon atom and a vacant orbital at the metal. 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The polarization of the orbital towards the carbon center is consistent with the observed nucleophilic character of the carbene complexes described here.</description><subject>Catalysis</subject><subject>Chemical Sciences</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2010</creationdate><recordtype>article</recordtype><recordid>eNpFkU1Lw0AQhhdRrFbBXyB7s4LV_chus960Wq0U6kG9hs1mQleSbN1NxHro0d9tSmuFGeZleHguL0InlFxSwtVVqqiIZPy-gw5oNBj0FePR7jYz2UGHIbwTwhgRbB91WBu5iuUB-nmeuTCfOd8EHGqd2sJ-Q4aN9ilUgI0r5wV8QbjGqV1xq610DTizurKuwmFR1TMINlxgD9rU9tPWC6yrDN-NXlplk1kI2OV4uhwup_jbeuMq25S98dv5v_4I7eW6CHC8uV30Orp_GT72J9OH8fBm0jecyrovFTEkAymzXJBcpLkxgtGUcmgzi4SUBgByZZQWisWmnXygJROxEZmUMe-i87V3potk7m2p_SJx2iaPN5Nk9SNEcM6i-JO27NmanXv30UCok9IGA0WhK3BNSAacS6VIHLVkb00a70LwkG_VlCSrgpLbdUFPLXq6kTZpCdkW_GuE_wLKZ40U</recordid><startdate>20100114</startdate><enddate>20100114</enddate><creator>Heuclin, Hadrien</creator><creator>Grünstein, Dan</creator><creator>Le Goff, Xavier-Frederic</creator><creator>Le Floch, Pascal</creator><creator>Mézailles, Nicolas</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>1XC</scope><orcidid>https://orcid.org/0000-0002-5041-0468</orcidid><orcidid>https://orcid.org/0000-0001-8735-6285</orcidid></search><sort><creationdate>20100114</creationdate><title>Phosphorus stabilized carbene complexes: bisphosphonate dianion synthesis, reactivity and DFT studies of O~C~O zirconium(IV) complexes</title><author>Heuclin, Hadrien ; Grünstein, Dan ; Le Goff, Xavier-Frederic ; Le Floch, Pascal ; Mézailles, Nicolas</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c316t-690c0de66df50f5bfcc521b13e5bf24566ceeef9c9a5928c28cf7a6258c5d6683</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2010</creationdate><topic>Catalysis</topic><topic>Chemical Sciences</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Heuclin, Hadrien</creatorcontrib><creatorcontrib>Grünstein, Dan</creatorcontrib><creatorcontrib>Le Goff, Xavier-Frederic</creatorcontrib><creatorcontrib>Le Floch, Pascal</creatorcontrib><creatorcontrib>Mézailles, Nicolas</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>Hyper Article en Ligne (HAL)</collection><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Heuclin, Hadrien</au><au>Grünstein, Dan</au><au>Le Goff, Xavier-Frederic</au><au>Le Floch, Pascal</au><au>Mézailles, Nicolas</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Phosphorus stabilized carbene complexes: bisphosphonate dianion synthesis, reactivity and DFT studies of O~C~O zirconium(IV) complexes</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><addtitle>Dalton Trans</addtitle><date>2010-01-14</date><risdate>2010</risdate><volume>39</volume><issue>2</issue><spage>492</spage><epage>499</epage><pages>492-499</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>The reactivity of the geminal dianion of tetraisopropyl methylenediphosphonate, 3, with [ZrCl4(THF)2] affords a trinuclear structure 5 in which an unprecedented triscarbene-Zr dianionic fragment is found. The overall trinuclear arrangement is assembled by PO bridging moieties. The X-ray crystal structure of 5 is presented. The reaction of complex 5 with stoichiometric amounts of pyridine affords a dinuclear complex 6 whose formulation was ascertained by an X-ray crystal structure. Complexes 5 and 6 cleanly react with aldehydes (R1)(H)CO to afford the corresponding olefin of general formula [((OiPr)2P=O)2C=C(R1)(H)]. DFT calculations which were carried out on the model complex of 5t and a hypothetical monometallic Zr complex [Zr(3)Cl2(OMe2)2] 8t indicate that the Zr-C bond only features a weak pi-interaction between the carbon atom and a vacant orbital at the metal. The polarization of the orbital towards the carbon center is consistent with the observed nucleophilic character of the carbene complexes described here.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>20023986</pmid><doi>10.1039/b915468j</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0002-5041-0468</orcidid><orcidid>https://orcid.org/0000-0001-8735-6285</orcidid></addata></record> |
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title | Phosphorus stabilized carbene complexes: bisphosphonate dianion synthesis, reactivity and DFT studies of O~C~O zirconium(IV) complexes |
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