Isolation of C1 through C4 derivatives from CO using heteroleptic uranium() metallocene aryloxide complexes
The conversion of C1 feedstock molecules such as CO into commodity chemicals is a desirable, but challenging, endeavour. When the U( iii ) complex, [(C 5 Me 5 ) 2 U(O-2,6- t Bu 2 -4-MeC 6 H 2 )], is exposed to 1 atm of CO, only coordination is observed by IR spectroscopy as well as X-ray crystallogr...
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description | The conversion of C1 feedstock molecules such as CO into commodity chemicals is a desirable, but challenging, endeavour. When the U(
iii
) complex, [(C
5
Me
5
)
2
U(O-2,6-
t
Bu
2
-4-MeC
6
H
2
)], is exposed to 1 atm of CO, only coordination is observed by IR spectroscopy as well as X-ray crystallography, unveiling a rare structurally characterized f element carbonyl. However, using [(C
5
Me
5
)
2
(MesO)U (THF)], Mes = 2,4,6-Me
3
C
6
H
2
, reaction with CO forms the bridging ethynediolate species, [{(C
5
Me
5
)
2
(MesO)U}
2
(μ
2
-OCCO)]. While ethynediolate complexes are known, their reactivity has not been reported in much detail to afford further functionalization. For example, addition of more CO to the ethynediolate complex with heating forms a ketene carboxylate, [{(C
5
Me
5
)
2
(MesO)U}
2
(
μ
2
:
κ
2
:
η
1
-C
3
O
3
)], which can be further reacted with CO
2
to yield a ketene dicarboxylate complex, [{(C
5
Me
5
)
2
(MesO)U}
2
(
μ
2
:
κ
2
:
κ
2
-C
4
O
5
)]. Since the ethynediolate showed reactivity with more CO, we explored its reactivity further. A [2 + 2] cycloaddition is observed with diphenylketene to yield [{(C
5
Me
5
)
2
U}
2
(OC(CPh
2
)C(&z.dbd;O)CO)] with concomitant formation of [(C
5
Me
5
)
2
U(OMes)
2
]. Surprisingly, reaction with SO
2
shows rare S-O bond cleavage to yield the unusual [(O
2
CC(O)(SO)]
2−
bridging ligand between two U(
iv
) centres. All complexes have been characterized using spectroscopic and structural methods, and the reaction of the ethynediolate with CO to form the ketene carboxylate has been investigated computationally as well as the reaction with SO
2
.
Functionalization of CO from C1 to C4 is acheived using a heteroleptic uranium(
iii
) complex. |
doi_str_mv | 10.1039/d2sc06375a |
format | Article |
fullrecord | <record><control><sourceid>proquest_hal_p</sourceid><recordid>TN_cdi_hal_primary_oai_HAL_hal_04218352v1</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2780484316</sourcerecordid><originalsourceid>FETCH-LOGICAL-c489t-f21d836ebac652b5cc8525e19178ad26ea939de7d3248ee2b54fbf3f2dbe8ffb3</originalsourceid><addsrcrecordid>eNpdkkFv1DAUhCMEolXphTvIgkuLtBDbcWJfkFah0Eor9QCcLcd53rg48WI7q_LvcZuyQH2x5fk0b_Q0RfESl-9xScWHnkRd1rRh6klxTMoKr2pGxdPDm5RHxWmMN2U-lGJGmufFEa15xQQWx8WPq-idStZPyBvUYpSG4OftgNoK9RDsPmt7iMgEP6L2Gs3RTls0QILgHeyS1WgOarLzeHaORkjKOa9hAqTCL-dvbQ9I-3Hn4Bbii-KZUS7C6cN9Unz_fPGtvVxtrr9ctevNSldcpJUhuOe0hk7pHL9jWnNGGGCBG656UoMSVPTQ9JRUHCATlekMNaTvgBvT0ZPi4-K7m7sR-hwnBeXkLtgxp5JeWfm_MtlBbv1eClHlSTQbvFkMfExWRm0T6EH7aQKdJBaEsqbJ0PkCDY-8L9cbefdXVgRzysgeZ_bsIVHwP2eISY42anBOTeDnKEnDy4pXFNcZffsIvfFzmPK-MtVwVmNSk0y9WygdfIwBzCEBLuVdL-Qn8rW978U6w6__3ccB_dOCDLxagBD1Qf1bLPobU0u9Ug</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2778561262</pqid></control><display><type>article</type><title>Isolation of C1 through C4 derivatives from CO using heteroleptic uranium() metallocene aryloxide complexes</title><source>DOAJ Directory of Open Access Journals</source><source>PubMed Central Open Access</source><source>EZB-FREE-00999 freely available EZB journals</source><source>PubMed Central</source><creator>Ward, Robert J ; Rosal, Iker del ; Kelley, Steven P ; Maron, Laurent ; Walensky, Justin R</creator><creatorcontrib>Ward, Robert J ; Rosal, Iker del ; Kelley, Steven P ; Maron, Laurent ; Walensky, Justin R ; Univ. of Missouri, Columbia, MO (United States)</creatorcontrib><description>The conversion of C1 feedstock molecules such as CO into commodity chemicals is a desirable, but challenging, endeavour. When the U(
iii
) complex, [(C
5
Me
5
)
2
U(O-2,6-
t
Bu
2
-4-MeC
6
H
2
)], is exposed to 1 atm of CO, only coordination is observed by IR spectroscopy as well as X-ray crystallography, unveiling a rare structurally characterized f element carbonyl. However, using [(C
5
Me
5
)
2
(MesO)U (THF)], Mes = 2,4,6-Me
3
C
6
H
2
, reaction with CO forms the bridging ethynediolate species, [{(C
5
Me
5
)
2
(MesO)U}
2
(μ
2
-OCCO)]. While ethynediolate complexes are known, their reactivity has not been reported in much detail to afford further functionalization. For example, addition of more CO to the ethynediolate complex with heating forms a ketene carboxylate, [{(C
5
Me
5
)
2
(MesO)U}
2
(
μ
2
:
κ
2
:
η
1
-C
3
O
3
)], which can be further reacted with CO
2
to yield a ketene dicarboxylate complex, [{(C
5
Me
5
)
2
(MesO)U}
2
(
μ
2
:
κ
2
:
κ
2
-C
4
O
5
)]. Since the ethynediolate showed reactivity with more CO, we explored its reactivity further. A [2 + 2] cycloaddition is observed with diphenylketene to yield [{(C
5
Me
5
)
2
U}
2
(OC(CPh
2
)C(&z.dbd;O)CO)] with concomitant formation of [(C
5
Me
5
)
2
U(OMes)
2
]. Surprisingly, reaction with SO
2
shows rare S-O bond cleavage to yield the unusual [(O
2
CC(O)(SO)]
2−
bridging ligand between two U(
iv
) centres. All complexes have been characterized using spectroscopic and structural methods, and the reaction of the ethynediolate with CO to form the ketene carboxylate has been investigated computationally as well as the reaction with SO
2
.
Functionalization of CO from C1 to C4 is acheived using a heteroleptic uranium(
iii
) complex.</description><identifier>ISSN: 2041-6520</identifier><identifier>EISSN: 2041-6539</identifier><identifier>DOI: 10.1039/d2sc06375a</identifier><identifier>PMID: 36845919</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Carbonyls ; Chemical Sciences ; Chemistry ; Crystallography ; Cycloaddition ; Infrared spectroscopy ; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY ; Reactivity ; Sulfur dioxide</subject><ispartof>Chemical science (Cambridge), 2023-02, Vol.14 (8), p.224-232</ispartof><rights>This journal is © The Royal Society of Chemistry.</rights><rights>Copyright Royal Society of Chemistry 2023</rights><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><rights>This journal is © The Royal Society of Chemistry 2023 The Royal Society of Chemistry</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c489t-f21d836ebac652b5cc8525e19178ad26ea939de7d3248ee2b54fbf3f2dbe8ffb3</citedby><cites>FETCH-LOGICAL-c489t-f21d836ebac652b5cc8525e19178ad26ea939de7d3248ee2b54fbf3f2dbe8ffb3</cites><orcidid>0000-0001-6755-4495 ; 0000-0003-2653-8557 ; 0000-0003-0221-2675 ; 0000-0001-6898-4550 ; 0000000326538557 ; 0000000302212675 ; 0000000167554495 ; 0000000168984550</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/PMC9945253/pdf/$$EPDF$$P50$$Gpubmedcentral$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC9945253/$$EHTML$$P50$$Gpubmedcentral$$Hfree_for_read</linktohtml><link.rule.ids>230,314,727,780,784,864,885,27924,27925,53791,53793</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/36845919$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://hal.science/hal-04218352$$DView record in HAL$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/biblio/1923577$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Ward, Robert J</creatorcontrib><creatorcontrib>Rosal, Iker del</creatorcontrib><creatorcontrib>Kelley, Steven P</creatorcontrib><creatorcontrib>Maron, Laurent</creatorcontrib><creatorcontrib>Walensky, Justin R</creatorcontrib><creatorcontrib>Univ. of Missouri, Columbia, MO (United States)</creatorcontrib><title>Isolation of C1 through C4 derivatives from CO using heteroleptic uranium() metallocene aryloxide complexes</title><title>Chemical science (Cambridge)</title><addtitle>Chem Sci</addtitle><description>The conversion of C1 feedstock molecules such as CO into commodity chemicals is a desirable, but challenging, endeavour. When the U(
iii
) complex, [(C
5
Me
5
)
2
U(O-2,6-
t
Bu
2
-4-MeC
6
H
2
)], is exposed to 1 atm of CO, only coordination is observed by IR spectroscopy as well as X-ray crystallography, unveiling a rare structurally characterized f element carbonyl. However, using [(C
5
Me
5
)
2
(MesO)U (THF)], Mes = 2,4,6-Me
3
C
6
H
2
, reaction with CO forms the bridging ethynediolate species, [{(C
5
Me
5
)
2
(MesO)U}
2
(μ
2
-OCCO)]. While ethynediolate complexes are known, their reactivity has not been reported in much detail to afford further functionalization. For example, addition of more CO to the ethynediolate complex with heating forms a ketene carboxylate, [{(C
5
Me
5
)
2
(MesO)U}
2
(
μ
2
:
κ
2
:
η
1
-C
3
O
3
)], which can be further reacted with CO
2
to yield a ketene dicarboxylate complex, [{(C
5
Me
5
)
2
(MesO)U}
2
(
μ
2
:
κ
2
:
κ
2
-C
4
O
5
)]. Since the ethynediolate showed reactivity with more CO, we explored its reactivity further. A [2 + 2] cycloaddition is observed with diphenylketene to yield [{(C
5
Me
5
)
2
U}
2
(OC(CPh
2
)C(&z.dbd;O)CO)] with concomitant formation of [(C
5
Me
5
)
2
U(OMes)
2
]. Surprisingly, reaction with SO
2
shows rare S-O bond cleavage to yield the unusual [(O
2
CC(O)(SO)]
2−
bridging ligand between two U(
iv
) centres. All complexes have been characterized using spectroscopic and structural methods, and the reaction of the ethynediolate with CO to form the ketene carboxylate has been investigated computationally as well as the reaction with SO
2
.
Functionalization of CO from C1 to C4 is acheived using a heteroleptic uranium(
iii
) complex.</description><subject>Carbonyls</subject><subject>Chemical Sciences</subject><subject>Chemistry</subject><subject>Crystallography</subject><subject>Cycloaddition</subject><subject>Infrared spectroscopy</subject><subject>INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY</subject><subject>Reactivity</subject><subject>Sulfur dioxide</subject><issn>2041-6520</issn><issn>2041-6539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><recordid>eNpdkkFv1DAUhCMEolXphTvIgkuLtBDbcWJfkFah0Eor9QCcLcd53rg48WI7q_LvcZuyQH2x5fk0b_Q0RfESl-9xScWHnkRd1rRh6klxTMoKr2pGxdPDm5RHxWmMN2U-lGJGmufFEa15xQQWx8WPq-idStZPyBvUYpSG4OftgNoK9RDsPmt7iMgEP6L2Gs3RTls0QILgHeyS1WgOarLzeHaORkjKOa9hAqTCL-dvbQ9I-3Hn4Bbii-KZUS7C6cN9Unz_fPGtvVxtrr9ctevNSldcpJUhuOe0hk7pHL9jWnNGGGCBG656UoMSVPTQ9JRUHCATlekMNaTvgBvT0ZPi4-K7m7sR-hwnBeXkLtgxp5JeWfm_MtlBbv1eClHlSTQbvFkMfExWRm0T6EH7aQKdJBaEsqbJ0PkCDY-8L9cbefdXVgRzysgeZ_bsIVHwP2eISY42anBOTeDnKEnDy4pXFNcZffsIvfFzmPK-MtVwVmNSk0y9WygdfIwBzCEBLuVdL-Qn8rW978U6w6__3ccB_dOCDLxagBD1Qf1bLPobU0u9Ug</recordid><startdate>20230222</startdate><enddate>20230222</enddate><creator>Ward, Robert J</creator><creator>Rosal, Iker del</creator><creator>Kelley, Steven P</creator><creator>Maron, Laurent</creator><creator>Walensky, Justin R</creator><general>Royal Society of Chemistry</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>1XC</scope><scope>VOOES</scope><scope>OTOTI</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0001-6755-4495</orcidid><orcidid>https://orcid.org/0000-0003-2653-8557</orcidid><orcidid>https://orcid.org/0000-0003-0221-2675</orcidid><orcidid>https://orcid.org/0000-0001-6898-4550</orcidid><orcidid>https://orcid.org/0000000326538557</orcidid><orcidid>https://orcid.org/0000000302212675</orcidid><orcidid>https://orcid.org/0000000167554495</orcidid><orcidid>https://orcid.org/0000000168984550</orcidid></search><sort><creationdate>20230222</creationdate><title>Isolation of C1 through C4 derivatives from CO using heteroleptic uranium() metallocene aryloxide complexes</title><author>Ward, Robert J ; Rosal, Iker del ; Kelley, Steven P ; Maron, Laurent ; Walensky, Justin R</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c489t-f21d836ebac652b5cc8525e19178ad26ea939de7d3248ee2b54fbf3f2dbe8ffb3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>Carbonyls</topic><topic>Chemical Sciences</topic><topic>Chemistry</topic><topic>Crystallography</topic><topic>Cycloaddition</topic><topic>Infrared spectroscopy</topic><topic>INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY</topic><topic>Reactivity</topic><topic>Sulfur dioxide</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Ward, Robert J</creatorcontrib><creatorcontrib>Rosal, Iker del</creatorcontrib><creatorcontrib>Kelley, Steven P</creatorcontrib><creatorcontrib>Maron, Laurent</creatorcontrib><creatorcontrib>Walensky, Justin R</creatorcontrib><creatorcontrib>Univ. of Missouri, Columbia, MO (United States)</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>Hyper Article en Ligne (HAL)</collection><collection>Hyper Article en Ligne (HAL) (Open Access)</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>Ward, Robert J</au><au>Rosal, Iker del</au><au>Kelley, Steven P</au><au>Maron, Laurent</au><au>Walensky, Justin R</au><aucorp>Univ. of Missouri, Columbia, MO (United States)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Isolation of C1 through C4 derivatives from CO using heteroleptic uranium() metallocene aryloxide complexes</atitle><jtitle>Chemical science (Cambridge)</jtitle><addtitle>Chem Sci</addtitle><date>2023-02-22</date><risdate>2023</risdate><volume>14</volume><issue>8</issue><spage>224</spage><epage>232</epage><pages>224-232</pages><issn>2041-6520</issn><eissn>2041-6539</eissn><abstract>The conversion of C1 feedstock molecules such as CO into commodity chemicals is a desirable, but challenging, endeavour. When the U(
iii
) complex, [(C
5
Me
5
)
2
U(O-2,6-
t
Bu
2
-4-MeC
6
H
2
)], is exposed to 1 atm of CO, only coordination is observed by IR spectroscopy as well as X-ray crystallography, unveiling a rare structurally characterized f element carbonyl. However, using [(C
5
Me
5
)
2
(MesO)U (THF)], Mes = 2,4,6-Me
3
C
6
H
2
, reaction with CO forms the bridging ethynediolate species, [{(C
5
Me
5
)
2
(MesO)U}
2
(μ
2
-OCCO)]. While ethynediolate complexes are known, their reactivity has not been reported in much detail to afford further functionalization. For example, addition of more CO to the ethynediolate complex with heating forms a ketene carboxylate, [{(C
5
Me
5
)
2
(MesO)U}
2
(
μ
2
:
κ
2
:
η
1
-C
3
O
3
)], which can be further reacted with CO
2
to yield a ketene dicarboxylate complex, [{(C
5
Me
5
)
2
(MesO)U}
2
(
μ
2
:
κ
2
:
κ
2
-C
4
O
5
)]. Since the ethynediolate showed reactivity with more CO, we explored its reactivity further. A [2 + 2] cycloaddition is observed with diphenylketene to yield [{(C
5
Me
5
)
2
U}
2
(OC(CPh
2
)C(&z.dbd;O)CO)] with concomitant formation of [(C
5
Me
5
)
2
U(OMes)
2
]. Surprisingly, reaction with SO
2
shows rare S-O bond cleavage to yield the unusual [(O
2
CC(O)(SO)]
2−
bridging ligand between two U(
iv
) centres. All complexes have been characterized using spectroscopic and structural methods, and the reaction of the ethynediolate with CO to form the ketene carboxylate has been investigated computationally as well as the reaction with SO
2
.
Functionalization of CO from C1 to C4 is acheived using a heteroleptic uranium(
iii
) complex.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>36845919</pmid><doi>10.1039/d2sc06375a</doi><tpages>9</tpages><orcidid>https://orcid.org/0000-0001-6755-4495</orcidid><orcidid>https://orcid.org/0000-0003-2653-8557</orcidid><orcidid>https://orcid.org/0000-0003-0221-2675</orcidid><orcidid>https://orcid.org/0000-0001-6898-4550</orcidid><orcidid>https://orcid.org/0000000326538557</orcidid><orcidid>https://orcid.org/0000000302212675</orcidid><orcidid>https://orcid.org/0000000167554495</orcidid><orcidid>https://orcid.org/0000000168984550</orcidid><oa>free_for_read</oa></addata></record> |
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source | DOAJ Directory of Open Access Journals; PubMed Central Open Access; EZB-FREE-00999 freely available EZB journals; PubMed Central |
subjects | Carbonyls Chemical Sciences Chemistry Crystallography Cycloaddition Infrared spectroscopy INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY Reactivity Sulfur dioxide |
title | Isolation of C1 through C4 derivatives from CO using heteroleptic uranium() metallocene aryloxide complexes |
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