Samarium(II) Monoalkyl Complex Supported by a β‐Diketiminato‐Based Tetradentate Ligand: Synthesis, Structure, and Catalytic Hydrosilylation of Internal Alkynes
The synthesis and catalytic applications of trivalent rare‐earth metal alkyl complexes have been well developed, but the chemistry of divalent rare‐earth metal alkyl complexes lagged much behind. Herein, we report the synthesis, structure, and catalytic applications of a samarium(II) monoalkyl compl...
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| Veröffentlicht in: | Chemistry : a European journal 2020-04, Vol.26 (24), p.5494-5499 |
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| creator | Liu, Xiaojuan Wen, Qingqing Xiang, Li Leng, Xuebing Chen, Yaofeng |
| description | The synthesis and catalytic applications of trivalent rare‐earth metal alkyl complexes have been well developed, but the chemistry of divalent rare‐earth metal alkyl complexes lagged much behind. Herein, we report the synthesis, structure, and catalytic applications of a samarium(II) monoalkyl complex supported by a β‐diketiminato‐based tetradentate ligand, [LSmCH(SiMe3)2] (L=[MeC(NDipp)CHC(Me)NCH2CH2N(Me)CH2CH2NMe2]−, Dipp=2,6‐(iPr)2C6H3). This complex is synthesized by the salt metathesis reaction of samarium iodide [LSm(μ‐I)]2 and KCH(SiMe3)2 in 63 % yield. Its structure is characterized by single‐crystal X‐ray diffraction, showing a distorted square‐pyramid coordination geometry. This samarium(II) monoalkyl complex exhibits high catalytic activity in the hydrosilylation of aryl and methyl‐substituted unsymmetrical internal alkynes with secondary hydrosilanes, selectively providing the α‐(E) products in high yields.
A five‐coordinate samarium(II) monoalkyl complex is synthesized and structurally characterized. This complex shows high catalytic activity and high stereo‐ and regioselectivity in the hydrosilylation of various aryl and methyl‐substituted unsymmetrical internal alkynes with secondary hydrosilanes under mild conditions (see scheme). |
| doi_str_mv | 10.1002/chem.202000342 |
| format | Article |
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A five‐coordinate samarium(II) monoalkyl complex is synthesized and structurally characterized. This complex shows high catalytic activity and high stereo‐ and regioselectivity in the hydrosilylation of various aryl and methyl‐substituted unsymmetrical internal alkynes with secondary hydrosilanes under mild conditions (see scheme).</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.202000342</identifier><identifier>PMID: 32157760</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>alkyl complex ; Alkynes ; Aromatic compounds ; Catalytic activity ; Chemical synthesis ; Chemistry ; Coordination compounds ; Crystal structure ; homogeneous catalysis ; Hydrosilylation ; Iodides ; Ligands ; Metathesis ; Samarium</subject><ispartof>Chemistry : a European journal, 2020-04, Vol.26 (24), p.5494-5499</ispartof><rights>2020 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c3732-6d23efca02f21718ee776322fa1813846898d585aedf72c239b13492067439f73</citedby><cites>FETCH-LOGICAL-c3732-6d23efca02f21718ee776322fa1813846898d585aedf72c239b13492067439f73</cites><orcidid>0000-0003-4664-8980</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%2Fchem.202000342$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.202000342$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27901,27902,45550,45551</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/32157760$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Liu, Xiaojuan</creatorcontrib><creatorcontrib>Wen, Qingqing</creatorcontrib><creatorcontrib>Xiang, Li</creatorcontrib><creatorcontrib>Leng, Xuebing</creatorcontrib><creatorcontrib>Chen, Yaofeng</creatorcontrib><title>Samarium(II) Monoalkyl Complex Supported by a β‐Diketiminato‐Based Tetradentate Ligand: Synthesis, Structure, and Catalytic Hydrosilylation of Internal Alkynes</title><title>Chemistry : a European journal</title><addtitle>Chemistry</addtitle><description>The synthesis and catalytic applications of trivalent rare‐earth metal alkyl complexes have been well developed, but the chemistry of divalent rare‐earth metal alkyl complexes lagged much behind. Herein, we report the synthesis, structure, and catalytic applications of a samarium(II) monoalkyl complex supported by a β‐diketiminato‐based tetradentate ligand, [LSmCH(SiMe3)2] (L=[MeC(NDipp)CHC(Me)NCH2CH2N(Me)CH2CH2NMe2]−, Dipp=2,6‐(iPr)2C6H3). This complex is synthesized by the salt metathesis reaction of samarium iodide [LSm(μ‐I)]2 and KCH(SiMe3)2 in 63 % yield. Its structure is characterized by single‐crystal X‐ray diffraction, showing a distorted square‐pyramid coordination geometry. This samarium(II) monoalkyl complex exhibits high catalytic activity in the hydrosilylation of aryl and methyl‐substituted unsymmetrical internal alkynes with secondary hydrosilanes, selectively providing the α‐(E) products in high yields.
A five‐coordinate samarium(II) monoalkyl complex is synthesized and structurally characterized. This complex shows high catalytic activity and high stereo‐ and regioselectivity in the hydrosilylation of various aryl and methyl‐substituted unsymmetrical internal alkynes with secondary hydrosilanes under mild conditions (see scheme).</description><subject>alkyl complex</subject><subject>Alkynes</subject><subject>Aromatic compounds</subject><subject>Catalytic activity</subject><subject>Chemical synthesis</subject><subject>Chemistry</subject><subject>Coordination compounds</subject><subject>Crystal structure</subject><subject>homogeneous catalysis</subject><subject>Hydrosilylation</subject><subject>Iodides</subject><subject>Ligands</subject><subject>Metathesis</subject><subject>Samarium</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNqFkc9u1DAQxi0EokvhyhFZ4lKkZvGfOE64lVDYlbbisOUceZMJdevYwXYEufEIPARPwIPwEDwJXm0pEhdOo9H85tN88yH0lJIlJYS9bK9gWDLCCCE8Z_fQggpGMy4LcR8tSJXLrBC8OkKPQrhOTFVw_hAdcUaFlAVZoO9bNSivp-FkvX6BL5x1ytzMBtduGA18wdtpHJ2P0OHdjBX--ePX129v9A1EPWirokvtaxXS-BKiVx3YqCLgjf6obPcKb2cbryDocIq30U9tnDyc4jTCtYrKzFG3eDV33gVtZqOidha7Hq9tBG-VwWfpFgvhMXrQKxPgyW09Rh_enl_Wq2zz_t26PttkLZecZUXHOPStIqxnVNISIHnkjPWKlpSXeVFWZSdKoaDrJWsZr3aU5xUjhcx51Ut-jE4OuqN3nyYIsRl0aMEYZcFNoWHpr4xzSUVCn_-DXrtpf_OeqrgQpBRFopYHqk0Wg4e-Gb1O_54bSpp9fs0-v-Yuv7Tw7FZ22g3Q3eF_AktAdQA-awPzf-SaenV-8Vf8N9I9qnc</recordid><startdate>20200424</startdate><enddate>20200424</enddate><creator>Liu, Xiaojuan</creator><creator>Wen, Qingqing</creator><creator>Xiang, Li</creator><creator>Leng, Xuebing</creator><creator>Chen, Yaofeng</creator><general>Wiley Subscription Services, Inc</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0003-4664-8980</orcidid></search><sort><creationdate>20200424</creationdate><title>Samarium(II) Monoalkyl Complex Supported by a β‐Diketiminato‐Based Tetradentate Ligand: Synthesis, Structure, and Catalytic Hydrosilylation of Internal Alkynes</title><author>Liu, Xiaojuan ; Wen, Qingqing ; Xiang, Li ; Leng, Xuebing ; Chen, Yaofeng</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3732-6d23efca02f21718ee776322fa1813846898d585aedf72c239b13492067439f73</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>alkyl complex</topic><topic>Alkynes</topic><topic>Aromatic compounds</topic><topic>Catalytic activity</topic><topic>Chemical synthesis</topic><topic>Chemistry</topic><topic>Coordination compounds</topic><topic>Crystal structure</topic><topic>homogeneous catalysis</topic><topic>Hydrosilylation</topic><topic>Iodides</topic><topic>Ligands</topic><topic>Metathesis</topic><topic>Samarium</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Liu, Xiaojuan</creatorcontrib><creatorcontrib>Wen, Qingqing</creatorcontrib><creatorcontrib>Xiang, Li</creatorcontrib><creatorcontrib>Leng, Xuebing</creatorcontrib><creatorcontrib>Chen, Yaofeng</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Liu, Xiaojuan</au><au>Wen, Qingqing</au><au>Xiang, Li</au><au>Leng, Xuebing</au><au>Chen, Yaofeng</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Samarium(II) Monoalkyl Complex Supported by a β‐Diketiminato‐Based Tetradentate Ligand: Synthesis, Structure, and Catalytic Hydrosilylation of Internal Alkynes</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chemistry</addtitle><date>2020-04-24</date><risdate>2020</risdate><volume>26</volume><issue>24</issue><spage>5494</spage><epage>5499</epage><pages>5494-5499</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>The synthesis and catalytic applications of trivalent rare‐earth metal alkyl complexes have been well developed, but the chemistry of divalent rare‐earth metal alkyl complexes lagged much behind. Herein, we report the synthesis, structure, and catalytic applications of a samarium(II) monoalkyl complex supported by a β‐diketiminato‐based tetradentate ligand, [LSmCH(SiMe3)2] (L=[MeC(NDipp)CHC(Me)NCH2CH2N(Me)CH2CH2NMe2]−, Dipp=2,6‐(iPr)2C6H3). This complex is synthesized by the salt metathesis reaction of samarium iodide [LSm(μ‐I)]2 and KCH(SiMe3)2 in 63 % yield. Its structure is characterized by single‐crystal X‐ray diffraction, showing a distorted square‐pyramid coordination geometry. This samarium(II) monoalkyl complex exhibits high catalytic activity in the hydrosilylation of aryl and methyl‐substituted unsymmetrical internal alkynes with secondary hydrosilanes, selectively providing the α‐(E) products in high yields.
A five‐coordinate samarium(II) monoalkyl complex is synthesized and structurally characterized. This complex shows high catalytic activity and high stereo‐ and regioselectivity in the hydrosilylation of various aryl and methyl‐substituted unsymmetrical internal alkynes with secondary hydrosilanes under mild conditions (see scheme).</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>32157760</pmid><doi>10.1002/chem.202000342</doi><tpages>6</tpages><orcidid>https://orcid.org/0000-0003-4664-8980</orcidid></addata></record> |
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| subjects | alkyl complex Alkynes Aromatic compounds Catalytic activity Chemical synthesis Chemistry Coordination compounds Crystal structure homogeneous catalysis Hydrosilylation Iodides Ligands Metathesis Samarium |
| title | Samarium(II) Monoalkyl Complex Supported by a β‐Diketiminato‐Based Tetradentate Ligand: Synthesis, Structure, and Catalytic Hydrosilylation of Internal Alkynes |
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