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...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Dalton transactions : an international journal of inorganic chemistry 2010-01, Vol.39 (2), p.492-499
Hauptverfasser: Heuclin, Hadrien, Grünstein, Dan, Le Goff, Xavier-Frederic, Le Floch, Pascal, Mézailles, Nicolas
Format: Artikel
Sprache:eng
Schlagworte:
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
container_end_page 499
container_issue 2
container_start_page 492
container_title Dalton transactions : an international journal of inorganic chemistry
container_volume 39
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
format Article
fullrecord <record><control><sourceid>proquest_hal_p</sourceid><recordid>TN_cdi_hal_primary_oai_HAL_hal_00533248v1</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>733699084</sourcerecordid><originalsourceid>FETCH-LOGICAL-c316t-690c0de66df50f5bfcc521b13e5bf24566ceeef9c9a5928c28cf7a6258c5d6683</originalsourceid><addsrcrecordid>eNpFkU1Lw0AQhhdRrFbBXyB7s4LV_chus960Wq0U6kG9hs1mQleSbN1NxHro0d9tSmuFGeZleHguL0InlFxSwtVVqqiIZPy-gw5oNBj0FePR7jYz2UGHIbwTwhgRbB91WBu5iuUB-nmeuTCfOd8EHGqd2sJ-Q4aN9ilUgI0r5wV8QbjGqV1xq610DTizurKuwmFR1TMINlxgD9rU9tPWC6yrDN-NXlplk1kI2OV4uhwup_jbeuMq25S98dv5v_4I7eW6CHC8uV30Orp_GT72J9OH8fBm0jecyrovFTEkAymzXJBcpLkxgtGUcmgzi4SUBgByZZQWisWmnXygJROxEZmUMe-i87V3potk7m2p_SJx2iaPN5Nk9SNEcM6i-JO27NmanXv30UCok9IGA0WhK3BNSAacS6VIHLVkb00a70LwkG_VlCSrgpLbdUFPLXq6kTZpCdkW_GuE_wLKZ40U</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>733699084</pqid></control><display><type>article</type><title>Phosphorus stabilized carbene complexes: bisphosphonate dianion synthesis, reactivity and DFT studies of O~C~O zirconium(IV) complexes</title><source>Royal Society Of Chemistry Journals</source><source>Alma/SFX Local Collection</source><creator>Heuclin, Hadrien ; Grünstein, Dan ; Le Goff, Xavier-Frederic ; Le Floch, Pascal ; Mézailles, Nicolas</creator><creatorcontrib>Heuclin, Hadrien ; Grünstein, Dan ; Le Goff, Xavier-Frederic ; Le Floch, Pascal ; Mézailles, Nicolas</creatorcontrib><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.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/b915468j</identifier><identifier>PMID: 20023986</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Catalysis ; Chemical Sciences</subject><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2010-01, Vol.39 (2), p.492-499</ispartof><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c316t-690c0de66df50f5bfcc521b13e5bf24566ceeef9c9a5928c28cf7a6258c5d6683</citedby><cites>FETCH-LOGICAL-c316t-690c0de66df50f5bfcc521b13e5bf24566ceeef9c9a5928c28cf7a6258c5d6683</cites><orcidid>0000-0002-5041-0468 ; 0000-0001-8735-6285</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,315,782,786,887,27931,27932</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/20023986$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://hal.science/hal-00533248$$DView record in HAL$$Hfree_for_read</backlink></links><search><creatorcontrib>Heuclin, Hadrien</creatorcontrib><creatorcontrib>Grünstein, Dan</creatorcontrib><creatorcontrib>Le Goff, Xavier-Frederic</creatorcontrib><creatorcontrib>Le Floch, Pascal</creatorcontrib><creatorcontrib>Mézailles, Nicolas</creatorcontrib><title>Phosphorus stabilized carbene complexes: bisphosphonate dianion synthesis, reactivity and DFT studies of O~C~O zirconium(IV) complexes</title><title>Dalton transactions : an international journal of inorganic chemistry</title><addtitle>Dalton Trans</addtitle><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.</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>
fulltext fulltext
identifier ISSN: 1477-9226
ispartof Dalton transactions : an international journal of inorganic chemistry, 2010-01, Vol.39 (2), p.492-499
issn 1477-9226
1477-9234
language eng
recordid cdi_hal_primary_oai_HAL_hal_00533248v1
source Royal Society Of Chemistry Journals; Alma/SFX Local Collection
subjects Catalysis
Chemical Sciences
title Phosphorus stabilized carbene complexes: bisphosphonate dianion synthesis, reactivity and DFT studies of O~C~O zirconium(IV) complexes
url https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-05T11%3A25%3A00IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_hal_p&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Phosphorus%20stabilized%20carbene%20complexes:%20bisphosphonate%20dianion%20synthesis,%20reactivity%20and%20DFT%20studies%20of%20O~C~O%20zirconium(IV)%20complexes&rft.jtitle=Dalton%20transactions%20:%20an%20international%20journal%20of%20inorganic%20chemistry&rft.au=Heuclin,%20Hadrien&rft.date=2010-01-14&rft.volume=39&rft.issue=2&rft.spage=492&rft.epage=499&rft.pages=492-499&rft.issn=1477-9226&rft.eissn=1477-9234&rft_id=info:doi/10.1039/b915468j&rft_dat=%3Cproquest_hal_p%3E733699084%3C/proquest_hal_p%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=733699084&rft_id=info:pmid/20023986&rfr_iscdi=true