Triggering Electron Transfer in Co(I) Dimers: Computational Evidences for a Reversible Disproportionation Mechanism
An inner‐sphere disproportionation mechanism of the Co(I) precursor CoCl(PPh3)3 is described through a Density Functional Theory study. The essential role of oleylamine in this process is unravelled. A detailed analysis of the electronic structure of Cobalt dimers of the general formula Co2Cl2Ln (L=...
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| Veröffentlicht in: | Chemphyschem 2021-04, Vol.22 (8), p.788-795 |
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| creator | Guillaumont, Maya Fourré, Isabelle Pilmé, Julien Halbert, Stéphanie Gérard, Hélène |
| description | An inner‐sphere disproportionation mechanism of the Co(I) precursor CoCl(PPh3)3 is described through a Density Functional Theory study. The essential role of oleylamine in this process is unravelled. A detailed analysis of the electronic structure of Cobalt dimers of the general formula Co2Cl2Ln (L=NH3 and PH3) demonstrates that electron transfer is triggered by asymetric coordination of amine and phosphine to stabilize a mixed‐valence Co(II)−Co(0) dimer. This is consistent with the HSAB statement that both amine and phosphine ligands are required to stabilize the reaction products, respectively Co(II) and Co(0) centers. We propose a quasi‐athermic multi‐step disproportionation mechanism with low activation barriers where the electron transfer goes through simple ligand exchanges between Co.
Inner‐sphere electron transfer in dimers of Co(I) precursor CoCl(PPh3)3 is triggered by simple ligand exchanges between the Co centers, leading an asymetric coordination of amines and phosphines to stabilize, according to HSAB principles, a mixed‐valence Co(II)−Co(0) dimer. |
| doi_str_mv | 10.1002/cphc.202000965 |
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Inner‐sphere electron transfer in dimers of Co(I) precursor CoCl(PPh3)3 is triggered by simple ligand exchanges between the Co centers, leading an asymetric coordination of amines and phosphines to stabilize, according to HSAB principles, a mixed‐valence Co(II)−Co(0) dimer.</description><identifier>ISSN: 1439-4235</identifier><identifier>EISSN: 1439-7641</identifier><identifier>DOI: 10.1002/cphc.202000965</identifier><identifier>PMID: 33529486</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Ammonia ; Chemical Sciences ; Cobalt Dimers ; Density functional theory ; DFT ; Dimers ; Disproportionation ; Electron Transfer ; Electronic structure ; Electrons ; Inner-sphere ; Ligands ; Molecular structure ; Phosphines ; Reaction products</subject><ispartof>Chemphyschem, 2021-04, Vol.22 (8), p.788-795</ispartof><rights>2021 Wiley‐VCH GmbH</rights><rights>2021 Wiley-VCH GmbH.</rights><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4445-5c6ac55db149e14e2a9915ef535426db69104bd045b1f48ed53a5219631a984b3</citedby><cites>FETCH-LOGICAL-c4445-5c6ac55db149e14e2a9915ef535426db69104bd045b1f48ed53a5219631a984b3</cites><orcidid>0000-0002-1961-9204 ; 0000-0002-8557-186X ; 0000-0003-1938-668X ; 0000-0003-0421-4930 ; 0000-0002-8935-9591</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fcphc.202000965$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fcphc.202000965$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>230,314,776,780,881,1411,27901,27902,45550,45551</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/33529486$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://hal.sorbonne-universite.fr/hal-03957603$$DView record in HAL$$Hfree_for_read</backlink></links><search><creatorcontrib>Guillaumont, Maya</creatorcontrib><creatorcontrib>Fourré, Isabelle</creatorcontrib><creatorcontrib>Pilmé, Julien</creatorcontrib><creatorcontrib>Halbert, Stéphanie</creatorcontrib><creatorcontrib>Gérard, Hélène</creatorcontrib><title>Triggering Electron Transfer in Co(I) Dimers: Computational Evidences for a Reversible Disproportionation Mechanism</title><title>Chemphyschem</title><addtitle>Chemphyschem</addtitle><description>An inner‐sphere disproportionation mechanism of the Co(I) precursor CoCl(PPh3)3 is described through a Density Functional Theory study. The essential role of oleylamine in this process is unravelled. A detailed analysis of the electronic structure of Cobalt dimers of the general formula Co2Cl2Ln (L=NH3 and PH3) demonstrates that electron transfer is triggered by asymetric coordination of amine and phosphine to stabilize a mixed‐valence Co(II)−Co(0) dimer. This is consistent with the HSAB statement that both amine and phosphine ligands are required to stabilize the reaction products, respectively Co(II) and Co(0) centers. We propose a quasi‐athermic multi‐step disproportionation mechanism with low activation barriers where the electron transfer goes through simple ligand exchanges between Co.
Inner‐sphere electron transfer in dimers of Co(I) precursor CoCl(PPh3)3 is triggered by simple ligand exchanges between the Co centers, leading an asymetric coordination of amines and phosphines to stabilize, according to HSAB principles, a mixed‐valence Co(II)−Co(0) dimer.</description><subject>Ammonia</subject><subject>Chemical Sciences</subject><subject>Cobalt Dimers</subject><subject>Density functional theory</subject><subject>DFT</subject><subject>Dimers</subject><subject>Disproportionation</subject><subject>Electron Transfer</subject><subject>Electronic structure</subject><subject>Electrons</subject><subject>Inner-sphere</subject><subject>Ligands</subject><subject>Molecular structure</subject><subject>Phosphines</subject><subject>Reaction products</subject><issn>1439-4235</issn><issn>1439-7641</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNqF0ctvEzEQB2ALUdEHXDkiS1zaQ4LfG3OrltBUCgKhcLa83tnE1e56sbNB_e_rkDSVuHDxS59_Gs0g9J6SKSWEfXLDxk0ZYYQQreQrdEEF15NCCfr6eBaMy3N0mdJDNjNS0DfonHPJtJipC5RW0a_XEH2_xvMW3DaGHq-i7VMDEfsel-H6_gZ_8R3E9DnfumHc2q0PvW3xfOdr6B0k3ISILf4Ju6x81UL-kIYYhhD_0v2Cv4Hb2N6n7i06a2yb4N1xv0K_vs5X5WKy_H53X94uJ04IISfSKeukrCsqNFABzGpNJTSSS8FUXSlNiahqImRFGzGDWnIrGdWKU6tnouJX6OaQu7GtGaLvbHw0wXqzuF2a_RvhWhaK8B3N9vpgc9W_R0hb0_nkoG1tD2FMhuVuUSF4UWT68R_6EMaY-5GVpFLlNhciq-lBuRhSitCcKqDE7Edn9qMzp9HlDx-OsWPVQX3iz7PKQB_AH9_C43_iTPljUb6EPwGDf6P4</recordid><startdate>20210419</startdate><enddate>20210419</enddate><creator>Guillaumont, Maya</creator><creator>Fourré, Isabelle</creator><creator>Pilmé, Julien</creator><creator>Halbert, Stéphanie</creator><creator>Gérard, Hélène</creator><general>Wiley Subscription Services, Inc</general><general>Wiley-VCH Verlag</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>K9.</scope><scope>7X8</scope><scope>1XC</scope><orcidid>https://orcid.org/0000-0002-1961-9204</orcidid><orcidid>https://orcid.org/0000-0002-8557-186X</orcidid><orcidid>https://orcid.org/0000-0003-1938-668X</orcidid><orcidid>https://orcid.org/0000-0003-0421-4930</orcidid><orcidid>https://orcid.org/0000-0002-8935-9591</orcidid></search><sort><creationdate>20210419</creationdate><title>Triggering Electron Transfer in Co(I) Dimers: Computational Evidences for a Reversible Disproportionation Mechanism</title><author>Guillaumont, Maya ; Fourré, Isabelle ; Pilmé, Julien ; Halbert, Stéphanie ; Gérard, Hélène</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4445-5c6ac55db149e14e2a9915ef535426db69104bd045b1f48ed53a5219631a984b3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>Ammonia</topic><topic>Chemical Sciences</topic><topic>Cobalt Dimers</topic><topic>Density functional theory</topic><topic>DFT</topic><topic>Dimers</topic><topic>Disproportionation</topic><topic>Electron Transfer</topic><topic>Electronic structure</topic><topic>Electrons</topic><topic>Inner-sphere</topic><topic>Ligands</topic><topic>Molecular structure</topic><topic>Phosphines</topic><topic>Reaction products</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Guillaumont, Maya</creatorcontrib><creatorcontrib>Fourré, Isabelle</creatorcontrib><creatorcontrib>Pilmé, Julien</creatorcontrib><creatorcontrib>Halbert, Stéphanie</creatorcontrib><creatorcontrib>Gérard, Hélène</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><collection>Hyper Article en Ligne (HAL)</collection><jtitle>Chemphyschem</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Guillaumont, Maya</au><au>Fourré, Isabelle</au><au>Pilmé, Julien</au><au>Halbert, Stéphanie</au><au>Gérard, Hélène</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Triggering Electron Transfer in Co(I) Dimers: Computational Evidences for a Reversible Disproportionation Mechanism</atitle><jtitle>Chemphyschem</jtitle><addtitle>Chemphyschem</addtitle><date>2021-04-19</date><risdate>2021</risdate><volume>22</volume><issue>8</issue><spage>788</spage><epage>795</epage><pages>788-795</pages><issn>1439-4235</issn><eissn>1439-7641</eissn><abstract>An inner‐sphere disproportionation mechanism of the Co(I) precursor CoCl(PPh3)3 is described through a Density Functional Theory study. The essential role of oleylamine in this process is unravelled. A detailed analysis of the electronic structure of Cobalt dimers of the general formula Co2Cl2Ln (L=NH3 and PH3) demonstrates that electron transfer is triggered by asymetric coordination of amine and phosphine to stabilize a mixed‐valence Co(II)−Co(0) dimer. This is consistent with the HSAB statement that both amine and phosphine ligands are required to stabilize the reaction products, respectively Co(II) and Co(0) centers. We propose a quasi‐athermic multi‐step disproportionation mechanism with low activation barriers where the electron transfer goes through simple ligand exchanges between Co.
Inner‐sphere electron transfer in dimers of Co(I) precursor CoCl(PPh3)3 is triggered by simple ligand exchanges between the Co centers, leading an asymetric coordination of amines and phosphines to stabilize, according to HSAB principles, a mixed‐valence Co(II)−Co(0) dimer.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>33529486</pmid><doi>10.1002/cphc.202000965</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0002-1961-9204</orcidid><orcidid>https://orcid.org/0000-0002-8557-186X</orcidid><orcidid>https://orcid.org/0000-0003-1938-668X</orcidid><orcidid>https://orcid.org/0000-0003-0421-4930</orcidid><orcidid>https://orcid.org/0000-0002-8935-9591</orcidid></addata></record> |
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| subjects | Ammonia Chemical Sciences Cobalt Dimers Density functional theory DFT Dimers Disproportionation Electron Transfer Electronic structure Electrons Inner-sphere Ligands Molecular structure Phosphines Reaction products |
| title | Triggering Electron Transfer in Co(I) Dimers: Computational Evidences for a Reversible Disproportionation Mechanism |
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