Synthesis and electronic structure analysis of the actinide allenylidenes, [{(NR)}An(CCCPh)] (An = U, Th; R = SiMe)
The reaction of [AnCl(NR 2 ) 3 ] (An = U, Th, R = SiMe 3 ) with in situ generated lithium-3,3-diphenylcyclopropene results in the formation of [{(NR 2 ) 3 }An(CH&z.dbd;C&z.dbd;CPh 2 )] (An = U, 1 ; Th, 2 ) in good yields after work-up. Deprotonation of 1 or 2 with LDA/2.2.2-cryptand results...
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| Veröffentlicht in: | Chemical science (Cambridge) 2021-11, Vol.12 (43), p.14383-14388 |
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| creator | Kent, Greggory T Yu, Xiaojuan Wu, Guang Autschbach, Jochen Hayton, Trevor W |
| description | The reaction of [AnCl(NR
2
)
3
] (An = U, Th, R = SiMe
3
) with
in situ
generated lithium-3,3-diphenylcyclopropene results in the formation of [{(NR
2
)
3
}An(CH&z.dbd;C&z.dbd;CPh
2
)] (An = U,
1
; Th,
2
) in good yields after work-up. Deprotonation of
1
or
2
with LDA/2.2.2-cryptand results in formation of the anionic allenylidenes, [Li(2.2.2-cryptand)][{(NR
2
)
3
}An(CCCPh
2
)] (An = U,
3
; Th,
4
). The calculated
13
C NMR chemical shifts of the C
α
, C
β
, and C
γ
nuclei in
2
and
4
nicely reproduce the experimentally assigned order, and exhibit a characteristic spin-orbit induced downfield shift at C
α
due to involvement of the 5f orbitals in the Th-C bonds. Additionally, the bonding analyses for
3
and
4
show a delocalized multi-center character of the ligand π orbitals involving the actinide. While a single-triple-single-bond resonance structure (
e.g.
, An-C&z.tbd;C-CPh
2
) predominates, the An&z.dbd;C&z.dbd;C&z.dbd;CPh
2
resonance form contributes, as well, more so for
3
than for
4
.
The actinide allenylidenes [{(NR
2
)
3
}An(CCCPh
2
)]
−
(An = U, Th, R = SiMe
3
) feature significant ligand-to-metal donation bonding and partial An&z.dbd;C double bond character. |
| doi_str_mv | 10.1039/d1sc04666g |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_pubme</sourceid><recordid>TN_cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_8580070</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2623081001</sourcerecordid><originalsourceid>FETCH-LOGICAL-c455t-8aa4392ebcd6d2d735c8754e0749cafc0c6ad80c51a3122f2e75b1de7ca11be73</originalsourceid><addsrcrecordid>eNpdkttrFDEYxQdRbKl98V0J-rIrXc1lMskgFpZRq1AvdNsnkZD9JtNJmU1qkiks4v9u1q3rJS85cH6cJN9JUTwk-DnBrH7Rkgi4rKrq8k6xT3FJZhVn9d2dpnivOIzxCufFGOFU3C_2WCklrmW9X8TF2qXeRBuRdi0yg4EUvLOAYgojpDGYbOhhvSF8hzKLNCTrbJvFMBi3HrJ0Jh6hL98nH8-mP-Zu0jTN5376FU3mDr1CF0fovH-JzrJc2A9m-qC41-khmsPb_aC4ePvmvHk3O_108r6Zn86g5DzNpNYlq6lZQlu1tBWMgxS8NFiUNegOMFS6lRg40YxQ2lEj-JK0RoAmZGkEOyiOt7nX43JlWjAuBT2o62BXOqyV11b96zjbq0t_oySXGAucA55sA3xMVkWwyUAP3rk8JEUkFYLzDE1uTwn-22hiUisbwQyDdsaPUdGKMiwJxiSjT_9Dr_wY8nQzxWvOc1y1CXy2pSD4GIPpdjcmWG06V6_JovnV-UmGH__9xh36u-EMPNoCIcLO_fNp2E-NLa7T</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2595575565</pqid></control><display><type>article</type><title>Synthesis and electronic structure analysis of the actinide allenylidenes, [{(NR)}An(CCCPh)] (An = U, Th; R = SiMe)</title><source>DOAJ Directory of Open Access Journals</source><source>Elektronische Zeitschriftenbibliothek - Frei zugängliche E-Journals</source><source>PubMed Central Open Access</source><source>PubMed Central</source><creator>Kent, Greggory T ; Yu, Xiaojuan ; Wu, Guang ; Autschbach, Jochen ; Hayton, Trevor W</creator><creatorcontrib>Kent, Greggory T ; Yu, Xiaojuan ; Wu, Guang ; Autschbach, Jochen ; Hayton, Trevor W</creatorcontrib><description><![CDATA[The reaction of [AnCl(NR
2
)
3
] (An = U, Th, R = SiMe
3
) with
in situ
generated lithium-3,3-diphenylcyclopropene results in the formation of [{(NR
2
)
3
}An(CH&z.dbd;C&z.dbd;CPh
2
)] (An = U,
1
; Th,
2
) in good yields after work-up. Deprotonation of
1
or
2
with LDA/2.2.2-cryptand results in formation of the anionic allenylidenes, [Li(2.2.2-cryptand)][{(NR
2
)
3
}An(CCCPh
2
)] (An = U,
3
; Th,
4
). The calculated
13
C NMR chemical shifts of the C
α
, C
β
, and C
γ
nuclei in
2
and
4
nicely reproduce the experimentally assigned order, and exhibit a characteristic spin-orbit induced downfield shift at C
α
due to involvement of the 5f orbitals in the Th-C bonds. Additionally, the bonding analyses for
3
and
4
show a delocalized multi-center character of the ligand π orbitals involving the actinide. While a single-triple-single-bond resonance structure (
e.g.
, An-C&z.tbd;C-CPh
2
) predominates, the An&z.dbd;C&z.dbd;C&z.dbd;CPh
2
resonance form contributes, as well, more so for
3
than for
4
.
The actinide allenylidenes [{(NR
2
)
3
}An(CCCPh
2
)]
−
(An = U, Th, R = SiMe
3
) feature significant ligand-to-metal donation bonding and partial An&z.dbd;C double bond character.]]></description><identifier>ISSN: 2041-6520</identifier><identifier>EISSN: 2041-6539</identifier><identifier>DOI: 10.1039/d1sc04666g</identifier><identifier>PMID: 34880989</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Chemistry ; Electronic structure ; Lithium ; NMR ; Nuclear magnetic resonance ; Orbitals ; Resonance ; Structural analysis ; Thorium</subject><ispartof>Chemical science (Cambridge), 2021-11, Vol.12 (43), p.14383-14388</ispartof><rights>This journal is © The Royal Society of Chemistry.</rights><rights>Copyright Royal Society of Chemistry 2021</rights><rights>This journal is © The Royal Society of Chemistry 2021 The Royal Society of Chemistry</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c455t-8aa4392ebcd6d2d735c8754e0749cafc0c6ad80c51a3122f2e75b1de7ca11be73</citedby><cites>FETCH-LOGICAL-c455t-8aa4392ebcd6d2d735c8754e0749cafc0c6ad80c51a3122f2e75b1de7ca11be73</cites><orcidid>0000-0001-9412-6170 ; 0000-0001-9392-877X ; 0000-0002-9334-2530 ; 0000-0003-4370-1424 ; 0000000293342530 ; 0000000194126170 ; 0000000343701424 ; 000000019392877X</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC8580070/pdf/$$EPDF$$P50$$Gpubmedcentral$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC8580070/$$EHTML$$P50$$Gpubmedcentral$$Hfree_for_read</linktohtml><link.rule.ids>230,314,727,780,784,864,885,27923,27924,53790,53792</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/34880989$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/biblio/1827755$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Kent, Greggory T</creatorcontrib><creatorcontrib>Yu, Xiaojuan</creatorcontrib><creatorcontrib>Wu, Guang</creatorcontrib><creatorcontrib>Autschbach, Jochen</creatorcontrib><creatorcontrib>Hayton, Trevor W</creatorcontrib><title>Synthesis and electronic structure analysis of the actinide allenylidenes, [{(NR)}An(CCCPh)] (An = U, Th; R = SiMe)</title><title>Chemical science (Cambridge)</title><addtitle>Chem Sci</addtitle><description><![CDATA[The reaction of [AnCl(NR
2
)
3
] (An = U, Th, R = SiMe
3
) with
in situ
generated lithium-3,3-diphenylcyclopropene results in the formation of [{(NR
2
)
3
}An(CH&z.dbd;C&z.dbd;CPh
2
)] (An = U,
1
; Th,
2
) in good yields after work-up. Deprotonation of
1
or
2
with LDA/2.2.2-cryptand results in formation of the anionic allenylidenes, [Li(2.2.2-cryptand)][{(NR
2
)
3
}An(CCCPh
2
)] (An = U,
3
; Th,
4
). The calculated
13
C NMR chemical shifts of the C
α
, C
β
, and C
γ
nuclei in
2
and
4
nicely reproduce the experimentally assigned order, and exhibit a characteristic spin-orbit induced downfield shift at C
α
due to involvement of the 5f orbitals in the Th-C bonds. Additionally, the bonding analyses for
3
and
4
show a delocalized multi-center character of the ligand π orbitals involving the actinide. While a single-triple-single-bond resonance structure (
e.g.
, An-C&z.tbd;C-CPh
2
) predominates, the An&z.dbd;C&z.dbd;C&z.dbd;CPh
2
resonance form contributes, as well, more so for
3
than for
4
.
The actinide allenylidenes [{(NR
2
)
3
}An(CCCPh
2
)]
−
(An = U, Th, R = SiMe
3
) feature significant ligand-to-metal donation bonding and partial An&z.dbd;C double bond character.]]></description><subject>Chemistry</subject><subject>Electronic structure</subject><subject>Lithium</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>Orbitals</subject><subject>Resonance</subject><subject>Structural analysis</subject><subject>Thorium</subject><issn>2041-6520</issn><issn>2041-6539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNpdkttrFDEYxQdRbKl98V0J-rIrXc1lMskgFpZRq1AvdNsnkZD9JtNJmU1qkiks4v9u1q3rJS85cH6cJN9JUTwk-DnBrH7Rkgi4rKrq8k6xT3FJZhVn9d2dpnivOIzxCufFGOFU3C_2WCklrmW9X8TF2qXeRBuRdi0yg4EUvLOAYgojpDGYbOhhvSF8hzKLNCTrbJvFMBi3HrJ0Jh6hL98nH8-mP-Zu0jTN5376FU3mDr1CF0fovH-JzrJc2A9m-qC41-khmsPb_aC4ePvmvHk3O_108r6Zn86g5DzNpNYlq6lZQlu1tBWMgxS8NFiUNegOMFS6lRg40YxQ2lEj-JK0RoAmZGkEOyiOt7nX43JlWjAuBT2o62BXOqyV11b96zjbq0t_oySXGAucA55sA3xMVkWwyUAP3rk8JEUkFYLzDE1uTwn-22hiUisbwQyDdsaPUdGKMiwJxiSjT_9Dr_wY8nQzxWvOc1y1CXy2pSD4GIPpdjcmWG06V6_JovnV-UmGH__9xh36u-EMPNoCIcLO_fNp2E-NLa7T</recordid><startdate>20211110</startdate><enddate>20211110</enddate><creator>Kent, Greggory T</creator><creator>Yu, Xiaojuan</creator><creator>Wu, Guang</creator><creator>Autschbach, Jochen</creator><creator>Hayton, Trevor W</creator><general>Royal Society of Chemistry</general><general>Royal Society of Chemistry (RSC)</general><general>The Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>7X8</scope><scope>OTOTI</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0001-9412-6170</orcidid><orcidid>https://orcid.org/0000-0001-9392-877X</orcidid><orcidid>https://orcid.org/0000-0002-9334-2530</orcidid><orcidid>https://orcid.org/0000-0003-4370-1424</orcidid><orcidid>https://orcid.org/0000000293342530</orcidid><orcidid>https://orcid.org/0000000194126170</orcidid><orcidid>https://orcid.org/0000000343701424</orcidid><orcidid>https://orcid.org/000000019392877X</orcidid></search><sort><creationdate>20211110</creationdate><title>Synthesis and electronic structure analysis of the actinide allenylidenes, [{(NR)}An(CCCPh)] (An = U, Th; R = SiMe)</title><author>Kent, Greggory T ; Yu, Xiaojuan ; Wu, Guang ; Autschbach, Jochen ; Hayton, Trevor W</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c455t-8aa4392ebcd6d2d735c8754e0749cafc0c6ad80c51a3122f2e75b1de7ca11be73</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>Chemistry</topic><topic>Electronic structure</topic><topic>Lithium</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>Orbitals</topic><topic>Resonance</topic><topic>Structural analysis</topic><topic>Thorium</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kent, Greggory T</creatorcontrib><creatorcontrib>Yu, Xiaojuan</creatorcontrib><creatorcontrib>Wu, Guang</creatorcontrib><creatorcontrib>Autschbach, Jochen</creatorcontrib><creatorcontrib>Hayton, Trevor W</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>MEDLINE - Academic</collection><collection>OSTI.GOV</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Chemical science (Cambridge)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kent, Greggory T</au><au>Yu, Xiaojuan</au><au>Wu, Guang</au><au>Autschbach, Jochen</au><au>Hayton, Trevor W</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis and electronic structure analysis of the actinide allenylidenes, [{(NR)}An(CCCPh)] (An = U, Th; R = SiMe)</atitle><jtitle>Chemical science (Cambridge)</jtitle><addtitle>Chem Sci</addtitle><date>2021-11-10</date><risdate>2021</risdate><volume>12</volume><issue>43</issue><spage>14383</spage><epage>14388</epage><pages>14383-14388</pages><issn>2041-6520</issn><eissn>2041-6539</eissn><abstract><![CDATA[The reaction of [AnCl(NR
2
)
3
] (An = U, Th, R = SiMe
3
) with
in situ
generated lithium-3,3-diphenylcyclopropene results in the formation of [{(NR
2
)
3
}An(CH&z.dbd;C&z.dbd;CPh
2
)] (An = U,
1
; Th,
2
) in good yields after work-up. Deprotonation of
1
or
2
with LDA/2.2.2-cryptand results in formation of the anionic allenylidenes, [Li(2.2.2-cryptand)][{(NR
2
)
3
}An(CCCPh
2
)] (An = U,
3
; Th,
4
). The calculated
13
C NMR chemical shifts of the C
α
, C
β
, and C
γ
nuclei in
2
and
4
nicely reproduce the experimentally assigned order, and exhibit a characteristic spin-orbit induced downfield shift at C
α
due to involvement of the 5f orbitals in the Th-C bonds. Additionally, the bonding analyses for
3
and
4
show a delocalized multi-center character of the ligand π orbitals involving the actinide. While a single-triple-single-bond resonance structure (
e.g.
, An-C&z.tbd;C-CPh
2
) predominates, the An&z.dbd;C&z.dbd;C&z.dbd;CPh
2
resonance form contributes, as well, more so for
3
than for
4
.
The actinide allenylidenes [{(NR
2
)
3
}An(CCCPh
2
)]
−
(An = U, Th, R = SiMe
3
) feature significant ligand-to-metal donation bonding and partial An&z.dbd;C double bond character.]]></abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>34880989</pmid><doi>10.1039/d1sc04666g</doi><tpages>6</tpages><orcidid>https://orcid.org/0000-0001-9412-6170</orcidid><orcidid>https://orcid.org/0000-0001-9392-877X</orcidid><orcidid>https://orcid.org/0000-0002-9334-2530</orcidid><orcidid>https://orcid.org/0000-0003-4370-1424</orcidid><orcidid>https://orcid.org/0000000293342530</orcidid><orcidid>https://orcid.org/0000000194126170</orcidid><orcidid>https://orcid.org/0000000343701424</orcidid><orcidid>https://orcid.org/000000019392877X</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 2041-6520 |
| ispartof | Chemical science (Cambridge), 2021-11, Vol.12 (43), p.14383-14388 |
| issn | 2041-6520 2041-6539 |
| language | eng |
| recordid | cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_8580070 |
| source | DOAJ Directory of Open Access Journals; Elektronische Zeitschriftenbibliothek - Frei zugängliche E-Journals; PubMed Central Open Access; PubMed Central |
| subjects | Chemistry Electronic structure Lithium NMR Nuclear magnetic resonance Orbitals Resonance Structural analysis Thorium |
| title | Synthesis and electronic structure analysis of the actinide allenylidenes, [{(NR)}An(CCCPh)] (An = U, Th; R = SiMe) |
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