Covalency in Ce IV and U IV Halide and N‐Heterocyclic Carbene Bonds
Oxidative halogenation with trityl chloride provides convenient access to Ce IV and U IV chloroamides [M(N{SiMe 3 } 2 ) 3 Cl] and their N‐heterocyclic carbene derivatives, [M(L)(N{SiMe 3 } 2 ) 2 Cl] (L=OCMe 2 CH 2 (CNCH 2 CH 2 NDipp) Dipp=2,6‐ i Pr 2 C 6 H 3 ). Computational analysis of the bonding...
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| Veröffentlicht in: | Chemistry : a European journal 2010-08, Vol.16 (31), p.9623-9629 |
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| container_title | Chemistry : a European journal |
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| creator | Arnold, Polly L. Turner, Zoë R. Kaltsoyannis, Nikolas Pelekanaki, Panagiota Bellabarba, Ronan M. Tooze, Robert P. |
| description | Oxidative halogenation with trityl chloride provides convenient access to Ce
IV
and U
IV
chloroamides [M(N{SiMe
3
}
2
)
3
Cl] and their N‐heterocyclic carbene derivatives, [M(L)(N{SiMe
3
}
2
)
2
Cl] (L=OCMe
2
CH
2
(CNCH
2
CH
2
NDipp) Dipp=2,6‐
i
Pr
2
C
6
H
3
). Computational analysis of the bonding in these and a fluoro analogue, [U(L)(N{SiMe
3
}
2
)
2
F], provides new information on the covalency in this relative rare oxidation state for molecular cerium complexes. Computational studies reveal increased Mayer bond orders in the actinide carbene bond compared with the lanthanide carbene bond, and natural and atoms‐in‐molecules analyses suggest greater overall ionicity in the cerium complexes than in the uranium analogues. |
| doi_str_mv | 10.1002/chem.201001471 |
| format | Article |
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IV
and U
IV
chloroamides [M(N{SiMe
3
}
2
)
3
Cl] and their N‐heterocyclic carbene derivatives, [M(L)(N{SiMe
3
}
2
)
2
Cl] (L=OCMe
2
CH
2
(CNCH
2
CH
2
NDipp) Dipp=2,6‐
i
Pr
2
C
6
H
3
). Computational analysis of the bonding in these and a fluoro analogue, [U(L)(N{SiMe
3
}
2
)
2
F], provides new information on the covalency in this relative rare oxidation state for molecular cerium complexes. Computational studies reveal increased Mayer bond orders in the actinide carbene bond compared with the lanthanide carbene bond, and natural and atoms‐in‐molecules analyses suggest greater overall ionicity in the cerium complexes than in the uranium analogues.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.201001471</identifier><language>eng</language><ispartof>Chemistry : a European journal, 2010-08, Vol.16 (31), p.9623-9629</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c169t-e50505727bbf7476407fec9c85ccc6b633e1eb442e469c6b7c82b2d53c7576b43</citedby><cites>FETCH-LOGICAL-c169t-e50505727bbf7476407fec9c85ccc6b633e1eb442e469c6b7c82b2d53c7576b43</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27901,27902</link.rule.ids></links><search><creatorcontrib>Arnold, Polly L.</creatorcontrib><creatorcontrib>Turner, Zoë R.</creatorcontrib><creatorcontrib>Kaltsoyannis, Nikolas</creatorcontrib><creatorcontrib>Pelekanaki, Panagiota</creatorcontrib><creatorcontrib>Bellabarba, Ronan M.</creatorcontrib><creatorcontrib>Tooze, Robert P.</creatorcontrib><title>Covalency in Ce IV and U IV Halide and N‐Heterocyclic Carbene Bonds</title><title>Chemistry : a European journal</title><description>Oxidative halogenation with trityl chloride provides convenient access to Ce
IV
and U
IV
chloroamides [M(N{SiMe
3
}
2
)
3
Cl] and their N‐heterocyclic carbene derivatives, [M(L)(N{SiMe
3
}
2
)
2
Cl] (L=OCMe
2
CH
2
(CNCH
2
CH
2
NDipp) Dipp=2,6‐
i
Pr
2
C
6
H
3
). Computational analysis of the bonding in these and a fluoro analogue, [U(L)(N{SiMe
3
}
2
)
2
F], provides new information on the covalency in this relative rare oxidation state for molecular cerium complexes. Computational studies reveal increased Mayer bond orders in the actinide carbene bond compared with the lanthanide carbene bond, and natural and atoms‐in‐molecules analyses suggest greater overall ionicity in the cerium complexes than in the uranium analogues.</description><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2010</creationdate><recordtype>article</recordtype><recordid>eNo9kM9Kw0AQhxdRMFavnvcFEvf_do8aqikUvVivYXcywUiayG4RevMRfEafxKSKzGG-3-8wDB8h15wVnDFxA6-4KwSbmCvLT0jGteC5tEafkow5ZXOjpTsnFym9McackTIjq3L88D0OcKDdQEuk6xfqh4ZuZ6h83zV4zI_fn18V7jGOcIC-A1r6GHBAejcOTbokZ63vE1797QXZ3q-eyyrfPD2sy9tNDty4fY6aTWOFDaG1yhrFbIvgYKkBwITpIeQYlBKojJsKC0sRRKMlWG1NUHJBit-7EMeUIrb1e-x2Ph5qzupZQj1LqP8lyB8kp07Y</recordid><startdate>20100816</startdate><enddate>20100816</enddate><creator>Arnold, Polly L.</creator><creator>Turner, Zoë R.</creator><creator>Kaltsoyannis, Nikolas</creator><creator>Pelekanaki, Panagiota</creator><creator>Bellabarba, Ronan M.</creator><creator>Tooze, Robert P.</creator><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20100816</creationdate><title>Covalency in Ce IV and U IV Halide and N‐Heterocyclic Carbene Bonds</title><author>Arnold, Polly L. ; Turner, Zoë R. ; Kaltsoyannis, Nikolas ; Pelekanaki, Panagiota ; Bellabarba, Ronan M. ; Tooze, Robert P.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c169t-e50505727bbf7476407fec9c85ccc6b633e1eb442e469c6b7c82b2d53c7576b43</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2010</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Arnold, Polly L.</creatorcontrib><creatorcontrib>Turner, Zoë R.</creatorcontrib><creatorcontrib>Kaltsoyannis, Nikolas</creatorcontrib><creatorcontrib>Pelekanaki, Panagiota</creatorcontrib><creatorcontrib>Bellabarba, Ronan M.</creatorcontrib><creatorcontrib>Tooze, Robert P.</creatorcontrib><collection>CrossRef</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Arnold, Polly L.</au><au>Turner, Zoë R.</au><au>Kaltsoyannis, Nikolas</au><au>Pelekanaki, Panagiota</au><au>Bellabarba, Ronan M.</au><au>Tooze, Robert P.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Covalency in Ce IV and U IV Halide and N‐Heterocyclic Carbene Bonds</atitle><jtitle>Chemistry : a European journal</jtitle><date>2010-08-16</date><risdate>2010</risdate><volume>16</volume><issue>31</issue><spage>9623</spage><epage>9629</epage><pages>9623-9629</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>Oxidative halogenation with trityl chloride provides convenient access to Ce
IV
and U
IV
chloroamides [M(N{SiMe
3
}
2
)
3
Cl] and their N‐heterocyclic carbene derivatives, [M(L)(N{SiMe
3
}
2
)
2
Cl] (L=OCMe
2
CH
2
(CNCH
2
CH
2
NDipp) Dipp=2,6‐
i
Pr
2
C
6
H
3
). Computational analysis of the bonding in these and a fluoro analogue, [U(L)(N{SiMe
3
}
2
)
2
F], provides new information on the covalency in this relative rare oxidation state for molecular cerium complexes. Computational studies reveal increased Mayer bond orders in the actinide carbene bond compared with the lanthanide carbene bond, and natural and atoms‐in‐molecules analyses suggest greater overall ionicity in the cerium complexes than in the uranium analogues.</abstract><doi>10.1002/chem.201001471</doi><tpages>7</tpages></addata></record> |
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| identifier | ISSN: 0947-6539 |
| ispartof | Chemistry : a European journal, 2010-08, Vol.16 (31), p.9623-9629 |
| issn | 0947-6539 1521-3765 |
| language | eng |
| recordid | cdi_crossref_primary_10_1002_chem_201001471 |
| source | Wiley Online Library Journals Frontfile Complete |
| title | Covalency in Ce IV and U IV Halide and N‐Heterocyclic Carbene Bonds |
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