A Germylene Stabilized by Homoconjugation
The synthesis of a bicyclic germylene from the reaction of a germole dianion with hafnocene dichloride is reported. This germylene is stabilized by a homoconjugative interaction of the dicoordinated germanium atom with a remote C=C double bond. First reactivity studies revealed its nucleophilic char...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2016-12, Vol.55 (51), p.15899-15904 |
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| creator | Dong, Zhaowen Reinhold, Crispin R. W. Schmidtmann, Marc Müller, Thomas |
| description | The synthesis of a bicyclic germylene from the reaction of a germole dianion with hafnocene dichloride is reported. This germylene is stabilized by a homoconjugative interaction of the dicoordinated germanium atom with a remote C=C double bond. First reactivity studies revealed its nucleophilic character and resulted in the synthesis of bimetallic hafnium/iron and hafnium/tungsten complexes with a germylene group linker.
A germane approach to stabilization: A germylene stabilized by homoconjugation is described. The structural parameters and a theoretical analysis of the bonding situation revealed a homoconjugative interaction between the C=C bond and the empty Ge 4p orbital. Reactivity studies confirmed its nucleophilic character, and bimetallic hafnium/iron and hafnium/tungsten complexes were synthesized. |
| doi_str_mv | 10.1002/anie.201609576 |
| format | Article |
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A germane approach to stabilization: A germylene stabilized by homoconjugation is described. The structural parameters and a theoretical analysis of the bonding situation revealed a homoconjugative interaction between the C=C bond and the empty Ge 4p orbital. Reactivity studies confirmed its nucleophilic character, and bimetallic hafnium/iron and hafnium/tungsten complexes were synthesized.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201609576</identifier><identifier>PMID: 27860046</identifier><identifier>CODEN: ACIEAY</identifier><language>eng</language><publisher>Germany: Blackwell Publishing Ltd</publisher><subject>carbene analogues ; germanium ; homoconjugation ; hyperconjugation ; X-ray diffraction</subject><ispartof>Angewandte Chemie International Edition, 2016-12, Vol.55 (51), p.15899-15904</ispartof><rights>2016 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><rights>2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c6546-e87c8975db28f1c1913b9610f02540e989f2f37cbb339e6ec9303abea84480e33</citedby><cites>FETCH-LOGICAL-c6546-e87c8975db28f1c1913b9610f02540e989f2f37cbb339e6ec9303abea84480e33</cites><orcidid>0000-0003-3985-7741 ; 0000-0001-8026-7271 ; 0000-0001-6163-470X ; 0000-0002-4247-3776</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.201609576$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.201609576$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/27860046$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Dong, Zhaowen</creatorcontrib><creatorcontrib>Reinhold, Crispin R. W.</creatorcontrib><creatorcontrib>Schmidtmann, Marc</creatorcontrib><creatorcontrib>Müller, Thomas</creatorcontrib><title>A Germylene Stabilized by Homoconjugation</title><title>Angewandte Chemie International Edition</title><addtitle>Angew. Chem. Int. Ed</addtitle><description>The synthesis of a bicyclic germylene from the reaction of a germole dianion with hafnocene dichloride is reported. This germylene is stabilized by a homoconjugative interaction of the dicoordinated germanium atom with a remote C=C double bond. First reactivity studies revealed its nucleophilic character and resulted in the synthesis of bimetallic hafnium/iron and hafnium/tungsten complexes with a germylene group linker.
A germane approach to stabilization: A germylene stabilized by homoconjugation is described. The structural parameters and a theoretical analysis of the bonding situation revealed a homoconjugative interaction between the C=C bond and the empty Ge 4p orbital. Reactivity studies confirmed its nucleophilic character, and bimetallic hafnium/iron and hafnium/tungsten complexes were synthesized.</description><subject>carbene analogues</subject><subject>germanium</subject><subject>homoconjugation</subject><subject>hyperconjugation</subject><subject>X-ray diffraction</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2016</creationdate><recordtype>article</recordtype><recordid>eNqF0EtLw0AUBeBBFFurW5cScKOL1Hkk81iWUtNK0YIVl8MkvZHUPGomQeOvNzW1iBtXcxffOQwHoXOChwRjemPyBIYUE46VL_gB6hOfEpcJwQ7b22PMFdInPXRi7br1UmJ-jHpUSI6xx_voeuQEUGZNCjk4j5UJkzT5hJUTNs60yIqoyNf1i6mSIj9FR7FJLZzt3gF6up0sx1N3_hDMxqO5G3Hf4y5IEUkl_FVIZUwioggLFSc4xtT3MCipYhozEYUhYwo4RIphZkIw0vMkBsYG6Krr3ZTFWw220lliI0hTk0NRW02kRyQmvuQtvfxD10Vd5u3vtkpKQui3GnYqKgtrS4j1pkwyUzaaYL0dUW9H1PsR28DFrrYOM1jt-c9qLVAdeE9SaP6p06P72eR3udtlE1vBxz5rylfNBRO-fr4PtFhMl-IuoHrBvgCXX4pr</recordid><startdate>20161219</startdate><enddate>20161219</enddate><creator>Dong, Zhaowen</creator><creator>Reinhold, Crispin R. W.</creator><creator>Schmidtmann, Marc</creator><creator>Müller, Thomas</creator><general>Blackwell Publishing Ltd</general><general>Wiley Subscription Services, Inc</general><scope>BSCLL</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0003-3985-7741</orcidid><orcidid>https://orcid.org/0000-0001-8026-7271</orcidid><orcidid>https://orcid.org/0000-0001-6163-470X</orcidid><orcidid>https://orcid.org/0000-0002-4247-3776</orcidid></search><sort><creationdate>20161219</creationdate><title>A Germylene Stabilized by Homoconjugation</title><author>Dong, Zhaowen ; Reinhold, Crispin R. W. ; Schmidtmann, Marc ; Müller, Thomas</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c6546-e87c8975db28f1c1913b9610f02540e989f2f37cbb339e6ec9303abea84480e33</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2016</creationdate><topic>carbene analogues</topic><topic>germanium</topic><topic>homoconjugation</topic><topic>hyperconjugation</topic><topic>X-ray diffraction</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Dong, Zhaowen</creatorcontrib><creatorcontrib>Reinhold, Crispin R. W.</creatorcontrib><creatorcontrib>Schmidtmann, Marc</creatorcontrib><creatorcontrib>Müller, Thomas</creatorcontrib><collection>Istex</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Dong, Zhaowen</au><au>Reinhold, Crispin R. W.</au><au>Schmidtmann, Marc</au><au>Müller, Thomas</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A Germylene Stabilized by Homoconjugation</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew. Chem. Int. Ed</addtitle><date>2016-12-19</date><risdate>2016</risdate><volume>55</volume><issue>51</issue><spage>15899</spage><epage>15904</epage><pages>15899-15904</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><coden>ACIEAY</coden><abstract>The synthesis of a bicyclic germylene from the reaction of a germole dianion with hafnocene dichloride is reported. This germylene is stabilized by a homoconjugative interaction of the dicoordinated germanium atom with a remote C=C double bond. First reactivity studies revealed its nucleophilic character and resulted in the synthesis of bimetallic hafnium/iron and hafnium/tungsten complexes with a germylene group linker.
A germane approach to stabilization: A germylene stabilized by homoconjugation is described. The structural parameters and a theoretical analysis of the bonding situation revealed a homoconjugative interaction between the C=C bond and the empty Ge 4p orbital. Reactivity studies confirmed its nucleophilic character, and bimetallic hafnium/iron and hafnium/tungsten complexes were synthesized.</abstract><cop>Germany</cop><pub>Blackwell Publishing Ltd</pub><pmid>27860046</pmid><doi>10.1002/anie.201609576</doi><tpages>6</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0003-3985-7741</orcidid><orcidid>https://orcid.org/0000-0001-8026-7271</orcidid><orcidid>https://orcid.org/0000-0001-6163-470X</orcidid><orcidid>https://orcid.org/0000-0002-4247-3776</orcidid></addata></record> |
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| subjects | carbene analogues germanium homoconjugation hyperconjugation X-ray diffraction |
| title | A Germylene Stabilized by Homoconjugation |
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