Metathesis of a UV imido complex: a route to a terminal UV sulfide
The metathesis reaction of a U V imido complex supported by sterically demanding tris( tert -butoxy)siloxide ligands with CS 2 afforded a terminal U V thiocarbonate but metathesis with H 2 S afforded the first example of a terminal U V sulfide. Herein, we report the synthesis and characterisation of...
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creator | Kelly, Rory P Falcone, Marta Lamsfus, Carlos Alvarez Scopelliti, Rosario Maron, Laurent Meyer, Karsten Mazzanti, Marinella |
description | The metathesis reaction of a U
V
imido complex supported by sterically demanding tris(
tert
-butoxy)siloxide ligands with CS
2
afforded a terminal U
V
thiocarbonate but metathesis with H
2
S afforded the first example of a terminal U
V
sulfide.
Herein, we report the synthesis and characterisation of the first terminal uranium(
v
) sulfide and a related U
V
trithiocarbonate complex supported by sterically demanding tris(
tert
-butoxy)siloxide ligands. The reaction of the potassium-bound U
V
imido complex, [U(NAd){OSi(O
t
Bu)
3
}
4
K] (
4
), with CS
2
led to the isolation of perthiodicarbonate [K(18c6)]
2
[C
2
S
6
] (
6
), with concomitant formation of the U
IV
complex, [U{OSi(O
t
Bu)
3
}
4
], and S
Created by potrace 1.16, written by Peter Selinger 2001-2019
C
NAd. In contrast, the reaction of the U
V
imido complex, [K(2.2.2-cryptand)][U(NAd){OSi(O
t
Bu)
3
}
4
] (
5
), with one or two equivalents of CS
2
afforded the trithiocarbonate complex, [K(2.2.2-cryptand)][U(CS
3
){OSi(O
t
Bu)
3
}
4
] (
7
), which was isolated in 57% yield, with concomitant elimination of the admantyl thiocyanate product, S
C
NAd. Complex
7
is likely formed by fast nucleophilic addition of a U
V
terminal sulfide intermediate, resulting from the slow metathesis reaction of the imido complex with CS
2
, to a second CS
2
molecule. The addition of a solution of H
2
S in thf (1.3 eq.) to
4
afforded the first isolable U
V
terminal sulfide complex, [K(2.2.2-cryptand)][US{OSi(O
t
Bu)
3
}
4
] (
8
), in 41% yield. Based on DFT calculations, triple-bond character with a strong covalent interaction is suggested for the U–S bond in complex
7
. |
doi_str_mv | 10.1039/c7sc01111c |
format | Article |
fullrecord | <record><control><sourceid>proquest_pubme</sourceid><recordid>TN_cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_5607896</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>1946430744</sourcerecordid><originalsourceid>FETCH-LOGICAL-p209t-776e995d25ff305be1be4168ca1124c591c828072fd13af17bc82588511d14543</originalsourceid><addsrcrecordid>eNpVjMtKxDAUhoMozjDOxifo0k01J5emcSHoMF5gxI3jtqTpqRNpm9qkom9vxUHw3_yXc_gIOQV6DpTrC6uCpTDJHpA5owLSTHJ9-JcZnZFlCG90EucgmTomM5ZrRTXAnNw8YjRxh8GFxNeJSbYviWtd5RPr277Bz8tpG_wYMYl-ihGH1nWm-fkLY1O7Ck_IUW2agMu9L8j2dv28uk83T3cPq-tN2jOqY6pUhlrLism65lSWCCUKyHJrAJiwUoPNWU4VqyvgpgZVTl3muQSoQEjBF-Tql9uPZYuVxS4Opin6wbVm-Cq8ccX_S-d2xav_KGRGVa6zCXC2Bwz-fcQQi9YFi01jOvRjKECLTHCqhODfB0JkyQ</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1946430744</pqid></control><display><type>article</type><title>Metathesis of a UV imido complex: a route to a terminal UV sulfide</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>Kelly, Rory P ; Falcone, Marta ; Lamsfus, Carlos Alvarez ; Scopelliti, Rosario ; Maron, Laurent ; Meyer, Karsten ; Mazzanti, Marinella</creator><creatorcontrib>Kelly, Rory P ; Falcone, Marta ; Lamsfus, Carlos Alvarez ; Scopelliti, Rosario ; Maron, Laurent ; Meyer, Karsten ; Mazzanti, Marinella</creatorcontrib><description>The metathesis reaction of a U
V
imido complex supported by sterically demanding tris(
tert
-butoxy)siloxide ligands with CS
2
afforded a terminal U
V
thiocarbonate but metathesis with H
2
S afforded the first example of a terminal U
V
sulfide.
Herein, we report the synthesis and characterisation of the first terminal uranium(
v
) sulfide and a related U
V
trithiocarbonate complex supported by sterically demanding tris(
tert
-butoxy)siloxide ligands. The reaction of the potassium-bound U
V
imido complex, [U(NAd){OSi(O
t
Bu)
3
}
4
K] (
4
), with CS
2
led to the isolation of perthiodicarbonate [K(18c6)]
2
[C
2
S
6
] (
6
), with concomitant formation of the U
IV
complex, [U{OSi(O
t
Bu)
3
}
4
], and S
Created by potrace 1.16, written by Peter Selinger 2001-2019
C
NAd. In contrast, the reaction of the U
V
imido complex, [K(2.2.2-cryptand)][U(NAd){OSi(O
t
Bu)
3
}
4
] (
5
), with one or two equivalents of CS
2
afforded the trithiocarbonate complex, [K(2.2.2-cryptand)][U(CS
3
){OSi(O
t
Bu)
3
}
4
] (
7
), which was isolated in 57% yield, with concomitant elimination of the admantyl thiocyanate product, S
C
NAd. Complex
7
is likely formed by fast nucleophilic addition of a U
V
terminal sulfide intermediate, resulting from the slow metathesis reaction of the imido complex with CS
2
, to a second CS
2
molecule. The addition of a solution of H
2
S in thf (1.3 eq.) to
4
afforded the first isolable U
V
terminal sulfide complex, [K(2.2.2-cryptand)][US{OSi(O
t
Bu)
3
}
4
] (
8
), in 41% yield. Based on DFT calculations, triple-bond character with a strong covalent interaction is suggested for the U–S bond in complex
7
.</description><identifier>ISSN: 2041-6520</identifier><identifier>EISSN: 2041-6539</identifier><identifier>DOI: 10.1039/c7sc01111c</identifier><identifier>PMID: 28970911</identifier><language>eng</language><publisher>Royal Society of Chemistry</publisher><subject>Chemistry</subject><ispartof>Chemical science (Cambridge), 2017-08, Vol.8 (8), p.5319-5328</ispartof><rights>This journal is © The Royal Society of Chemistry 2017 2017</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC5607896/pdf/$$EPDF$$P50$$Gpubmedcentral$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC5607896/$$EHTML$$P50$$Gpubmedcentral$$Hfree_for_read</linktohtml><link.rule.ids>230,314,724,777,781,861,882,27905,27906,53772,53774</link.rule.ids></links><search><creatorcontrib>Kelly, Rory P</creatorcontrib><creatorcontrib>Falcone, Marta</creatorcontrib><creatorcontrib>Lamsfus, Carlos Alvarez</creatorcontrib><creatorcontrib>Scopelliti, Rosario</creatorcontrib><creatorcontrib>Maron, Laurent</creatorcontrib><creatorcontrib>Meyer, Karsten</creatorcontrib><creatorcontrib>Mazzanti, Marinella</creatorcontrib><title>Metathesis of a UV imido complex: a route to a terminal UV sulfide</title><title>Chemical science (Cambridge)</title><description>The metathesis reaction of a U
V
imido complex supported by sterically demanding tris(
tert
-butoxy)siloxide ligands with CS
2
afforded a terminal U
V
thiocarbonate but metathesis with H
2
S afforded the first example of a terminal U
V
sulfide.
Herein, we report the synthesis and characterisation of the first terminal uranium(
v
) sulfide and a related U
V
trithiocarbonate complex supported by sterically demanding tris(
tert
-butoxy)siloxide ligands. The reaction of the potassium-bound U
V
imido complex, [U(NAd){OSi(O
t
Bu)
3
}
4
K] (
4
), with CS
2
led to the isolation of perthiodicarbonate [K(18c6)]
2
[C
2
S
6
] (
6
), with concomitant formation of the U
IV
complex, [U{OSi(O
t
Bu)
3
}
4
], and S
Created by potrace 1.16, written by Peter Selinger 2001-2019
C
NAd. In contrast, the reaction of the U
V
imido complex, [K(2.2.2-cryptand)][U(NAd){OSi(O
t
Bu)
3
}
4
] (
5
), with one or two equivalents of CS
2
afforded the trithiocarbonate complex, [K(2.2.2-cryptand)][U(CS
3
){OSi(O
t
Bu)
3
}
4
] (
7
), which was isolated in 57% yield, with concomitant elimination of the admantyl thiocyanate product, S
C
NAd. Complex
7
is likely formed by fast nucleophilic addition of a U
V
terminal sulfide intermediate, resulting from the slow metathesis reaction of the imido complex with CS
2
, to a second CS
2
molecule. The addition of a solution of H
2
S in thf (1.3 eq.) to
4
afforded the first isolable U
V
terminal sulfide complex, [K(2.2.2-cryptand)][US{OSi(O
t
Bu)
3
}
4
] (
8
), in 41% yield. Based on DFT calculations, triple-bond character with a strong covalent interaction is suggested for the U–S bond in complex
7
.</description><subject>Chemistry</subject><issn>2041-6520</issn><issn>2041-6539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><recordid>eNpVjMtKxDAUhoMozjDOxifo0k01J5emcSHoMF5gxI3jtqTpqRNpm9qkom9vxUHw3_yXc_gIOQV6DpTrC6uCpTDJHpA5owLSTHJ9-JcZnZFlCG90EucgmTomM5ZrRTXAnNw8YjRxh8GFxNeJSbYviWtd5RPr277Bz8tpG_wYMYl-ihGH1nWm-fkLY1O7Ck_IUW2agMu9L8j2dv28uk83T3cPq-tN2jOqY6pUhlrLism65lSWCCUKyHJrAJiwUoPNWU4VqyvgpgZVTl3muQSoQEjBF-Tql9uPZYuVxS4Opin6wbVm-Cq8ccX_S-d2xav_KGRGVa6zCXC2Bwz-fcQQi9YFi01jOvRjKECLTHCqhODfB0JkyQ</recordid><startdate>20170801</startdate><enddate>20170801</enddate><creator>Kelly, Rory P</creator><creator>Falcone, Marta</creator><creator>Lamsfus, Carlos Alvarez</creator><creator>Scopelliti, Rosario</creator><creator>Maron, Laurent</creator><creator>Meyer, Karsten</creator><creator>Mazzanti, Marinella</creator><general>Royal Society of Chemistry</general><scope>7X8</scope><scope>5PM</scope></search><sort><creationdate>20170801</creationdate><title>Metathesis of a UV imido complex: a route to a terminal UV sulfide</title><author>Kelly, Rory P ; Falcone, Marta ; Lamsfus, Carlos Alvarez ; Scopelliti, Rosario ; Maron, Laurent ; Meyer, Karsten ; Mazzanti, Marinella</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-p209t-776e995d25ff305be1be4168ca1124c591c828072fd13af17bc82588511d14543</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><topic>Chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kelly, Rory P</creatorcontrib><creatorcontrib>Falcone, Marta</creatorcontrib><creatorcontrib>Lamsfus, Carlos Alvarez</creatorcontrib><creatorcontrib>Scopelliti, Rosario</creatorcontrib><creatorcontrib>Maron, Laurent</creatorcontrib><creatorcontrib>Meyer, Karsten</creatorcontrib><creatorcontrib>Mazzanti, Marinella</creatorcontrib><collection>MEDLINE - Academic</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>Kelly, Rory P</au><au>Falcone, Marta</au><au>Lamsfus, Carlos Alvarez</au><au>Scopelliti, Rosario</au><au>Maron, Laurent</au><au>Meyer, Karsten</au><au>Mazzanti, Marinella</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Metathesis of a UV imido complex: a route to a terminal UV sulfide</atitle><jtitle>Chemical science (Cambridge)</jtitle><date>2017-08-01</date><risdate>2017</risdate><volume>8</volume><issue>8</issue><spage>5319</spage><epage>5328</epage><pages>5319-5328</pages><issn>2041-6520</issn><eissn>2041-6539</eissn><abstract>The metathesis reaction of a U
V
imido complex supported by sterically demanding tris(
tert
-butoxy)siloxide ligands with CS
2
afforded a terminal U
V
thiocarbonate but metathesis with H
2
S afforded the first example of a terminal U
V
sulfide.
Herein, we report the synthesis and characterisation of the first terminal uranium(
v
) sulfide and a related U
V
trithiocarbonate complex supported by sterically demanding tris(
tert
-butoxy)siloxide ligands. The reaction of the potassium-bound U
V
imido complex, [U(NAd){OSi(O
t
Bu)
3
}
4
K] (
4
), with CS
2
led to the isolation of perthiodicarbonate [K(18c6)]
2
[C
2
S
6
] (
6
), with concomitant formation of the U
IV
complex, [U{OSi(O
t
Bu)
3
}
4
], and S
Created by potrace 1.16, written by Peter Selinger 2001-2019
C
NAd. In contrast, the reaction of the U
V
imido complex, [K(2.2.2-cryptand)][U(NAd){OSi(O
t
Bu)
3
}
4
] (
5
), with one or two equivalents of CS
2
afforded the trithiocarbonate complex, [K(2.2.2-cryptand)][U(CS
3
){OSi(O
t
Bu)
3
}
4
] (
7
), which was isolated in 57% yield, with concomitant elimination of the admantyl thiocyanate product, S
C
NAd. Complex
7
is likely formed by fast nucleophilic addition of a U
V
terminal sulfide intermediate, resulting from the slow metathesis reaction of the imido complex with CS
2
, to a second CS
2
molecule. The addition of a solution of H
2
S in thf (1.3 eq.) to
4
afforded the first isolable U
V
terminal sulfide complex, [K(2.2.2-cryptand)][US{OSi(O
t
Bu)
3
}
4
] (
8
), in 41% yield. Based on DFT calculations, triple-bond character with a strong covalent interaction is suggested for the U–S bond in complex
7
.</abstract><pub>Royal Society of Chemistry</pub><pmid>28970911</pmid><doi>10.1039/c7sc01111c</doi><tpages>10</tpages><oa>free_for_read</oa></addata></record> |
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language | eng |
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source | DOAJ Directory of Open Access Journals; Elektronische Zeitschriftenbibliothek - Frei zugängliche E-Journals; PubMed Central Open Access; PubMed Central |
subjects | Chemistry |
title | Metathesis of a UV imido complex: a route to a terminal UV sulfide |
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