Synthetic, structural and reaction chemistry of N-heterocyclic germylene and stannylene compounds featuring N-boryl substituents
This study details the syntheses of N-heterocyclic germylenes and stannylenes featuring diazaborolyl groups, {(HCDippN)2B} (Dipp = 2,6-iPr2C6H3), as both of the N-bound substituents, with a view to generating electron rich and sterically protected metal centres. The energies of their key frontier or...
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| Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2019-08, Vol.48 (31), p.11951-11960 |
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| container_title | Dalton transactions : an international journal of inorganic chemistry |
| container_volume | 48 |
| creator | Kristinsdóttir, Lilja Oldroyd, Nicola L Grabiner, Rachel Knights, Alastair W Heilmann, Andreas Protchenko, Andrey V Niu, Haoyu Kolychev, Eugene L Campos, Jesús Hicks, Jamie Christensen, Kirsten E Aldridge, Simon |
| description | This study details the syntheses of N-heterocyclic germylenes and stannylenes featuring diazaborolyl groups, {(HCDippN)2B} (Dipp = 2,6-iPr2C6H3), as both of the N-bound substituents, with a view to generating electron rich and sterically protected metal centres. The energies of their key frontier orbitals - the group 14-centred lone pair and orthogonal pπ-orbital (typically the HOMO-2 and LUMO) have been probed by DFT calculations and compared with a related acyclic analogue, revealing (in the case of the stannylenes) a correlation with the measured 119Sn chemical shifts. The reactivity of the germylene systems towards oxygen atom transfer agents has been examined, with 2 : 1 reaction stoichiometries being observed for both Me3NO and pyridine N-oxide, leading to the formation of products thought to be derived from the activation of C-H bonds by a transient first-formed germanone. |
| doi_str_mv | 10.1039/c9dt02449b |
| format | Article |
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The energies of their key frontier orbitals - the group 14-centred lone pair and orthogonal pπ-orbital (typically the HOMO-2 and LUMO) have been probed by DFT calculations and compared with a related acyclic analogue, revealing (in the case of the stannylenes) a correlation with the measured 119Sn chemical shifts. The reactivity of the germylene systems towards oxygen atom transfer agents has been examined, with 2 : 1 reaction stoichiometries being observed for both Me3NO and pyridine N-oxide, leading to the formation of products thought to be derived from the activation of C-H bonds by a transient first-formed germanone.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/c9dt02449b</identifier><identifier>PMID: 31318369</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Correlation analysis ; Crystal structure ; Crystallography ; Mathematical analysis ; Molecular orbitals ; Organic chemistry ; Stoichiometry</subject><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2019-08, Vol.48 (31), p.11951-11960</ispartof><rights>Copyright Royal Society of Chemistry 2019</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c315t-395bb128d23d9872fc132567963962a1d4adddaa7f5a771bddf07590ddd1aad83</citedby><cites>FETCH-LOGICAL-c315t-395bb128d23d9872fc132567963962a1d4adddaa7f5a771bddf07590ddd1aad83</cites><orcidid>0000-0001-9998-9434 ; 0000-0001-5495-1846 ; 0000-0001-9450-2594 ; 0000-0002-5155-1262</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/31318369$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Kristinsdóttir, Lilja</creatorcontrib><creatorcontrib>Oldroyd, Nicola L</creatorcontrib><creatorcontrib>Grabiner, Rachel</creatorcontrib><creatorcontrib>Knights, Alastair W</creatorcontrib><creatorcontrib>Heilmann, Andreas</creatorcontrib><creatorcontrib>Protchenko, Andrey V</creatorcontrib><creatorcontrib>Niu, Haoyu</creatorcontrib><creatorcontrib>Kolychev, Eugene L</creatorcontrib><creatorcontrib>Campos, Jesús</creatorcontrib><creatorcontrib>Hicks, Jamie</creatorcontrib><creatorcontrib>Christensen, Kirsten E</creatorcontrib><creatorcontrib>Aldridge, Simon</creatorcontrib><title>Synthetic, structural and reaction chemistry of N-heterocyclic germylene and stannylene compounds featuring N-boryl substituents</title><title>Dalton transactions : an international journal of inorganic chemistry</title><addtitle>Dalton Trans</addtitle><description>This study details the syntheses of N-heterocyclic germylenes and stannylenes featuring diazaborolyl groups, {(HCDippN)2B} (Dipp = 2,6-iPr2C6H3), as both of the N-bound substituents, with a view to generating electron rich and sterically protected metal centres. The energies of their key frontier orbitals - the group 14-centred lone pair and orthogonal pπ-orbital (typically the HOMO-2 and LUMO) have been probed by DFT calculations and compared with a related acyclic analogue, revealing (in the case of the stannylenes) a correlation with the measured 119Sn chemical shifts. The reactivity of the germylene systems towards oxygen atom transfer agents has been examined, with 2 : 1 reaction stoichiometries being observed for both Me3NO and pyridine N-oxide, leading to the formation of products thought to be derived from the activation of C-H bonds by a transient first-formed germanone.</description><subject>Correlation analysis</subject><subject>Crystal structure</subject><subject>Crystallography</subject><subject>Mathematical analysis</subject><subject>Molecular orbitals</subject><subject>Organic chemistry</subject><subject>Stoichiometry</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNpdkTtPwzAUhS0EolBY-AHIEgtCBPzIyyOUp1TBQJkjx3baVIld_Biy8dMxbenA5Gvf7x5dnwPAGUY3GFF2K5j0iKQpq_fAEU6LImGEpvu7muQjcOzcEiFCUEYOwYhiikuasyPw_TFov1C-FdfQeRuED5Z3kGsJreLCt0ZDsVB9G5sDNA18SyKtrBGD6FoB58r2Q6e0Wo84z7XeXIXpVyZo6WCjeBRt9TzO1sYOHXShdr71QWnvTsBBwzunTrfnGHw-Pc4mL8n0_fl1cjdNBMWZTyjL6hqTUhIqWVmQRmBKsrxgOWU54VimXErJedFkvChwLWWDioyh-Ig5lyUdg8uN7sqar6Ccr-KfhOo6rpUJriIkY4zgkrGIXvxDlyZYHbeLVF7m0epo4BhcbShhjXNWNdXKtj23Q4VR9ZtLNWEPs3Uu9xE-30qGuldyh_4FQX8AaQyLOA</recordid><startdate>20190821</startdate><enddate>20190821</enddate><creator>Kristinsdóttir, Lilja</creator><creator>Oldroyd, Nicola L</creator><creator>Grabiner, Rachel</creator><creator>Knights, Alastair W</creator><creator>Heilmann, Andreas</creator><creator>Protchenko, Andrey V</creator><creator>Niu, Haoyu</creator><creator>Kolychev, Eugene L</creator><creator>Campos, Jesús</creator><creator>Hicks, Jamie</creator><creator>Christensen, Kirsten E</creator><creator>Aldridge, Simon</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0001-9998-9434</orcidid><orcidid>https://orcid.org/0000-0001-5495-1846</orcidid><orcidid>https://orcid.org/0000-0001-9450-2594</orcidid><orcidid>https://orcid.org/0000-0002-5155-1262</orcidid></search><sort><creationdate>20190821</creationdate><title>Synthetic, structural and reaction chemistry of N-heterocyclic germylene and stannylene compounds featuring N-boryl substituents</title><author>Kristinsdóttir, Lilja ; 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The energies of their key frontier orbitals - the group 14-centred lone pair and orthogonal pπ-orbital (typically the HOMO-2 and LUMO) have been probed by DFT calculations and compared with a related acyclic analogue, revealing (in the case of the stannylenes) a correlation with the measured 119Sn chemical shifts. The reactivity of the germylene systems towards oxygen atom transfer agents has been examined, with 2 : 1 reaction stoichiometries being observed for both Me3NO and pyridine N-oxide, leading to the formation of products thought to be derived from the activation of C-H bonds by a transient first-formed germanone.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>31318369</pmid><doi>10.1039/c9dt02449b</doi><tpages>10</tpages><orcidid>https://orcid.org/0000-0001-9998-9434</orcidid><orcidid>https://orcid.org/0000-0001-5495-1846</orcidid><orcidid>https://orcid.org/0000-0001-9450-2594</orcidid><orcidid>https://orcid.org/0000-0002-5155-1262</orcidid></addata></record> |
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| source | Royal Society Of Chemistry Journals; Alma/SFX Local Collection |
| subjects | Correlation analysis Crystal structure Crystallography Mathematical analysis Molecular orbitals Organic chemistry Stoichiometry |
| title | Synthetic, structural and reaction chemistry of N-heterocyclic germylene and stannylene compounds featuring N-boryl substituents |
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