A Nonheme Thiolate-Ligated Cobalt Superoxo Complex: Synthesis and Spectroscopic Characterization, Computational Studies, and Hydrogen Atom Abstraction Reactivity
The synthesis and characterization of a Co(II) dithiolato complex Co(Me TACN)(S SiMe ) (1) are reported. Reaction of 1 with O generates a rare thiolate-ligated cobalt-superoxo species Co(O )(Me TACN)(S SiMe ) (2) that was characterized spectroscopically and structurally by resonance Raman, EPR, and...
Gespeichert in:
| Veröffentlicht in: | Journal of the American Chemical Society Jg. 141; H. 8; S. 3641 |
|---|---|
| Hauptverfasser: | , , , , , |
| Format: | Journal Article |
| Sprache: | Englisch |
| Veröffentlicht: |
United States
27.02.2019
|
| ISSN: | 1520-5126, 1520-5126 |
| Online-Zugang: | Weitere Angaben |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| Abstract | The synthesis and characterization of a Co(II) dithiolato complex Co(Me
TACN)(S
SiMe
) (1) are reported. Reaction of 1 with O
generates a rare thiolate-ligated cobalt-superoxo species Co(O
)(Me
TACN)(S
SiMe
) (2) that was characterized spectroscopically and structurally by resonance Raman, EPR, and X-ray absorption spectroscopies as well as density functional theory. Metal-superoxo species are proposed to S-oxygenate metal-bound thiolate donors in nonheme thiol dioxygenases, but 2 does not lead to S-oxygenation of the intramolecular thiolate donors and does not react with exogenous sulfur donors. However, complex 2 is capable of oxidizing the O-H bonds of 2,2,6,6-tetramethylpiperidin-1-ol derivatives via H atom abstraction. Complementary proton-coupled electron-transfer reactivity is seen for 2 with separated proton/reductant pairs. The reactivity studies indicate that 2 can abstract H atoms from weak X-H bonds with bond dissociation free energy (BDFE) ≤ 70 kcal mol
. DFT calculations predict that the putative Co(OOH) product has an O-H BDFE = 67 kcal mol
, which matches the observed pattern of reactivity seen for 2. These data provide new information regarding the selectivity of S-oxygenation versus H atom abstraction in thiolate-ligated nonheme metalloenzymes that react with O
. |
|---|---|
| AbstractList | The synthesis and characterization of a Co(II) dithiolato complex Co(Me3TACN)(S2SiMe2) (1) are reported. Reaction of 1 with O2 generates a rare thiolate-ligated cobalt-superoxo species Co(O2)(Me3TACN)(S2SiMe2) (2) that was characterized spectroscopically and structurally by resonance Raman, EPR, and X-ray absorption spectroscopies as well as density functional theory. Metal-superoxo species are proposed to S-oxygenate metal-bound thiolate donors in nonheme thiol dioxygenases, but 2 does not lead to S-oxygenation of the intramolecular thiolate donors and does not react with exogenous sulfur donors. However, complex 2 is capable of oxidizing the O-H bonds of 2,2,6,6-tetramethylpiperidin-1-ol derivatives via H atom abstraction. Complementary proton-coupled electron-transfer reactivity is seen for 2 with separated proton/reductant pairs. The reactivity studies indicate that 2 can abstract H atoms from weak X-H bonds with bond dissociation free energy (BDFE) ≤ 70 kcal mol-1. DFT calculations predict that the putative Co(OOH) product has an O-H BDFE = 67 kcal mol-1, which matches the observed pattern of reactivity seen for 2. These data provide new information regarding the selectivity of S-oxygenation versus H atom abstraction in thiolate-ligated nonheme metalloenzymes that react with O2.The synthesis and characterization of a Co(II) dithiolato complex Co(Me3TACN)(S2SiMe2) (1) are reported. Reaction of 1 with O2 generates a rare thiolate-ligated cobalt-superoxo species Co(O2)(Me3TACN)(S2SiMe2) (2) that was characterized spectroscopically and structurally by resonance Raman, EPR, and X-ray absorption spectroscopies as well as density functional theory. Metal-superoxo species are proposed to S-oxygenate metal-bound thiolate donors in nonheme thiol dioxygenases, but 2 does not lead to S-oxygenation of the intramolecular thiolate donors and does not react with exogenous sulfur donors. However, complex 2 is capable of oxidizing the O-H bonds of 2,2,6,6-tetramethylpiperidin-1-ol derivatives via H atom abstraction. Complementary proton-coupled electron-transfer reactivity is seen for 2 with separated proton/reductant pairs. The reactivity studies indicate that 2 can abstract H atoms from weak X-H bonds with bond dissociation free energy (BDFE) ≤ 70 kcal mol-1. DFT calculations predict that the putative Co(OOH) product has an O-H BDFE = 67 kcal mol-1, which matches the observed pattern of reactivity seen for 2. These data provide new information regarding the selectivity of S-oxygenation versus H atom abstraction in thiolate-ligated nonheme metalloenzymes that react with O2. The synthesis and characterization of a Co(II) dithiolato complex Co(Me TACN)(S SiMe ) (1) are reported. Reaction of 1 with O generates a rare thiolate-ligated cobalt-superoxo species Co(O )(Me TACN)(S SiMe ) (2) that was characterized spectroscopically and structurally by resonance Raman, EPR, and X-ray absorption spectroscopies as well as density functional theory. Metal-superoxo species are proposed to S-oxygenate metal-bound thiolate donors in nonheme thiol dioxygenases, but 2 does not lead to S-oxygenation of the intramolecular thiolate donors and does not react with exogenous sulfur donors. However, complex 2 is capable of oxidizing the O-H bonds of 2,2,6,6-tetramethylpiperidin-1-ol derivatives via H atom abstraction. Complementary proton-coupled electron-transfer reactivity is seen for 2 with separated proton/reductant pairs. The reactivity studies indicate that 2 can abstract H atoms from weak X-H bonds with bond dissociation free energy (BDFE) ≤ 70 kcal mol . DFT calculations predict that the putative Co(OOH) product has an O-H BDFE = 67 kcal mol , which matches the observed pattern of reactivity seen for 2. These data provide new information regarding the selectivity of S-oxygenation versus H atom abstraction in thiolate-ligated nonheme metalloenzymes that react with O . |
| Author | Goldberg, David P Gordon, Jesse B Moënne-Loccoz, Pierre Vilbert, Avery C Lancaster, Kyle M Siegler, Maxime A |
| Author_xml | – sequence: 1 givenname: Jesse B orcidid: 0000-0002-6331-7940 surname: Gordon fullname: Gordon, Jesse B organization: Department of Chemistry , The Johns Hopkins University , 3400 North Charles Street , Baltimore , Maryland 21218 , United States – sequence: 2 givenname: Avery C surname: Vilbert fullname: Vilbert, Avery C organization: Department of Chemistry and Chemical Biology, Baker Laboratory , Cornell University , Ithaca , New York 14853 , United States – sequence: 3 givenname: Maxime A surname: Siegler fullname: Siegler, Maxime A organization: Department of Chemistry , The Johns Hopkins University , 3400 North Charles Street , Baltimore , Maryland 21218 , United States – sequence: 4 givenname: Kyle M orcidid: 0000-0001-7296-128X surname: Lancaster fullname: Lancaster, Kyle M organization: Department of Chemistry and Chemical Biology, Baker Laboratory , Cornell University , Ithaca , New York 14853 , United States – sequence: 5 givenname: Pierre orcidid: 0000-0002-7684-7617 surname: Moënne-Loccoz fullname: Moënne-Loccoz, Pierre organization: Department of Biochemistry & Molecular Biology , Oregon Health & Science University , Portland , Oregon 97239-3098 , United States – sequence: 6 givenname: David P orcidid: 0000-0003-4645-1045 surname: Goldberg fullname: Goldberg, David P organization: Department of Chemistry , The Johns Hopkins University , 3400 North Charles Street , Baltimore , Maryland 21218 , United States |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/30776222$$D View this record in MEDLINE/PubMed |
| BookMark | eNpNkDtPwzAUhS1UxKOwMSOPDE3xq3HCVlW8pAokAnNkOzfUKIlD7KCWf8M_JS0gMZ1zpO-7wz1Go8Y1gNAZJVNKGL18U8ZPE0055WIPHdEZI9GMsnj0rx-iY-_fCCGCJfQAHXIiZcwYO0Jfc_zgmhXUgJ9X1lUqQLS0r0MUeOG0qgLO-hY6t3bDrtsK1lc42zRhBd56rJoCZy2Y0DlvXGsNXqxUp0yAzn6qYF0z2Wl92A1V4Sz0hQU_2al3m6Jzr9DgeXA1nmsftu4A4ifYlg8bNidov1SVh9PfHKOXm-vnxV20fLy9X8yXkRIyCZEGSkliqEgKkbJCGgNcJFLH0igjjea0lCmJ0wGWCopUwUybUqQlJ5qVnLMxuvi523buvQcf8tp6A1WlGnC9zxlNeCyEkOmAnv-iva6hyNvO1qrb5H9vZd_Enn89 |
| CitedBy_id | crossref_primary_10_1007_s00723_025_01794_9 crossref_primary_10_1021_jacs_4c05849 crossref_primary_10_1002_anie_202111492 crossref_primary_10_1002_adma_202403187 crossref_primary_10_1002_anie_202214074 crossref_primary_10_1021_jacs_9b12571 crossref_primary_10_3390_molecules27196416 crossref_primary_10_1134_S1070328421080078 crossref_primary_10_1016_j_ccr_2020_213761 crossref_primary_10_1002_anie_202409793 crossref_primary_10_1002_ange_202208143 crossref_primary_10_1021_jacs_9b05320 crossref_primary_10_1002_aic_18652 crossref_primary_10_1002_chem_202203579 crossref_primary_10_1021_jacs_4c18445 crossref_primary_10_1039_D2NR04830B crossref_primary_10_1002_ange_202111492 crossref_primary_10_1002_ejic_202300418 crossref_primary_10_1021_jacs_9b03329 crossref_primary_10_1021_jacs_4c01871 crossref_primary_10_1002_ange_202507578 crossref_primary_10_1021_jacs_3c12337 crossref_primary_10_1002_ange_202409793 crossref_primary_10_1002_ange_202214074 crossref_primary_10_1021_jacs_4c07335 crossref_primary_10_1039_D1SC01952J crossref_primary_10_1039_D2QI00741J crossref_primary_10_1002_anie_202208143 crossref_primary_10_1002_chem_202001818 crossref_primary_10_1021_jacs_9b05274 crossref_primary_10_1016_j_apcatb_2024_124513 crossref_primary_10_1016_j_molstruc_2024_139554 crossref_primary_10_1021_jacs_3c14422 crossref_primary_10_1021_jacs_9b11014 crossref_primary_10_1002_anie_202507578 crossref_primary_10_1007_s11426_021_1042_y crossref_primary_10_1016_j_jinorgbio_2024_112776 crossref_primary_10_1021_jacsau_5c00418 crossref_primary_10_1021_jacs_4c14877 crossref_primary_10_1360_SSC_2024_0121 |
| ContentType | Journal Article |
| DBID | NPM 7X8 |
| DOI | 10.1021/jacs.8b13134 |
| DatabaseName | PubMed MEDLINE - Academic |
| DatabaseTitle | PubMed MEDLINE - Academic |
| DatabaseTitleList | MEDLINE - Academic PubMed |
| Database_xml | – sequence: 1 dbid: NPM name: PubMed url: http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed sourceTypes: Index Database – sequence: 2 dbid: 7X8 name: MEDLINE - Academic url: https://search.proquest.com/medline sourceTypes: Aggregation Database |
| DeliveryMethod | no_fulltext_linktorsrc |
| Discipline | Chemistry |
| EISSN | 1520-5126 |
| ExternalDocumentID | 30776222 |
| Genre | Research Support, U.S. Gov't, Non-P.H.S Research Support, Non-U.S. Gov't Journal Article Research Support, N.I.H., Extramural |
| GrantInformation_xml | – fundername: NIGMS NIH HHS grantid: R01 GM119374 – fundername: NIGMS NIH HHS grantid: R35 GM124908 – fundername: NIGMS NIH HHS grantid: P41 GM103393 |
| GroupedDBID | --- -DZ -ET -~X .DC .K2 4.4 53G 55A 5GY 5RE 5VS 7~N 85S AABXI AAHBH ABJNI ABMVS ABPPZ ABQRX ABUCX ACBEA ACGFO ACGFS ACJ ACNCT ACS ADHLV AEESW AENEX AFEFF AGXLV AHGAQ ALMA_UNASSIGNED_HOLDINGS AQSVZ BAANH BKOMP CS3 CUPRZ DU5 EBS ED~ EJD F5P GGK GNL IH2 IH9 JG~ LG6 NPM P2P ROL RXW TAE TN5 UHB UI2 UKR UPT VF5 VG9 VQA W1F WH7 XSW YIN YQT YZZ ZCA ~02 7X8 AAYWT ABBLG ABLBI ABUFD AETEA AHDLI |
| ID | FETCH-LOGICAL-a478t-be1108c148d492d7cce3487b67cac7cb31f790694787aed9ae5bcf49f30b2f332 |
| IEDL.DBID | 7X8 |
| ISICitedReferencesCount | 49 |
| ISICitedReferencesURI | http://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=Summon&SrcAuth=ProQuest&DestLinkType=CitingArticles&DestApp=WOS_CPL&KeyUT=000460200100043&url=https%3A%2F%2Fcvtisr.summon.serialssolutions.com%2F%23%21%2Fsearch%3Fho%3Df%26include.ft.matches%3Dt%26l%3Dnull%26q%3D |
| ISSN | 1520-5126 |
| IngestDate | Sun Nov 09 12:09:57 EST 2025 Wed Feb 19 02:30:59 EST 2025 |
| IsPeerReviewed | true |
| IsScholarly | true |
| Issue | 8 |
| Language | English |
| LinkModel | DirectLink |
| MergedId | FETCHMERGED-LOGICAL-a478t-be1108c148d492d7cce3487b67cac7cb31f790694787aed9ae5bcf49f30b2f332 |
| Notes | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
| ORCID | 0000-0001-7296-128X 0000-0002-6331-7940 0000-0002-7684-7617 0000-0003-4645-1045 |
| PMID | 30776222 |
| PQID | 2183644479 |
| PQPubID | 23479 |
| ParticipantIDs | proquest_miscellaneous_2183644479 pubmed_primary_30776222 |
| PublicationCentury | 2000 |
| PublicationDate | 2019-02-27 |
| PublicationDateYYYYMMDD | 2019-02-27 |
| PublicationDate_xml | – month: 02 year: 2019 text: 2019-02-27 day: 27 |
| PublicationDecade | 2010 |
| PublicationPlace | United States |
| PublicationPlace_xml | – name: United States |
| PublicationTitle | Journal of the American Chemical Society |
| PublicationTitleAlternate | J Am Chem Soc |
| PublicationYear | 2019 |
| SSID | ssj0004281 |
| Score | 2.5005724 |
| Snippet | The synthesis and characterization of a Co(II) dithiolato complex Co(Me
TACN)(S
SiMe
) (1) are reported. Reaction of 1 with O
generates a rare thiolate-ligated... The synthesis and characterization of a Co(II) dithiolato complex Co(Me3TACN)(S2SiMe2) (1) are reported. Reaction of 1 with O2 generates a rare... |
| SourceID | proquest pubmed |
| SourceType | Aggregation Database Index Database |
| StartPage | 3641 |
| Title | A Nonheme Thiolate-Ligated Cobalt Superoxo Complex: Synthesis and Spectroscopic Characterization, Computational Studies, and Hydrogen Atom Abstraction Reactivity |
| URI | https://www.ncbi.nlm.nih.gov/pubmed/30776222 https://www.proquest.com/docview/2183644479 |
| Volume | 141 |
| WOSCitedRecordID | wos000460200100043&url=https%3A%2F%2Fcvtisr.summon.serialssolutions.com%2F%23%21%2Fsearch%3Fho%3Df%26include.ft.matches%3Dt%26l%3Dnull%26q%3D |
| hasFullText | |
| inHoldings | 1 |
| isFullTextHit | |
| isPrint | |
| link | http://cvtisr.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwpV1La9tAEF7auNBc0leaOn2whR69sWyttdpeijENPrTG1C74ZvYxS1xaybXkYP-c_NPMSHLbSyDQi5AOC2J3mPlmdub7GPsQfC8CbRPhI5BCJmEgjE2k8LGCNPImeG0qsQk1maSLhZ42Bbeiaas8-MTKUfvcUY28S6EcY7dU-tP6tyDVKLpdbSQ0HrJWjFCGWrrU4h-28H5a86ViioSBLWka3zGsdX8YV1yktofL5N3gsgoyl0_-9_eespMGXvJhbQ_P2APInrPHo4Oq2wt2M-STPMNv4POrFea1JYgvRLMBno-IG6Tksy2Rh-9yTr7iJ-w-8tk-Q5xYrApuMs9Jsr4kEsx8vXJ89IfxuR7o7PBaKKIpMvKmUbFTLR3v_SZHk-XDMv_Fh5bqLNVgBf8G9EJCFqfs--Xn-WgsGpkGYaRKS2GBRgkc5lVe6r5XzkGMaZBNlDNOORv3gtI0X4u-wQCePQysC1KHOLL9EMf9l-woyzN4xbjyXgeDCAmMkWlitLcDxJeRhIHyiQxt9v6w-0vcN7rbMBnk22L5d__b7Kw-wuW65utYxkRZhDjo_B6rX7NjhES6GlpXb1groBOAt-yRuy5XxeZdZV_4nEy_3gJ4BeAj |
| linkProvider | ProQuest |
| openUrl | ctx_ver=Z39.88-2004&ctx_enc=info%3Aofi%2Fenc%3AUTF-8&rfr_id=info%3Asid%2Fsummon.serialssolutions.com&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Ajournal&rft.genre=article&rft.atitle=A+Nonheme+Thiolate-Ligated+Cobalt+Superoxo+Complex%3A+Synthesis+and+Spectroscopic+Characterization%2C+Computational+Studies%2C+and+Hydrogen+Atom+Abstraction+Reactivity&rft.jtitle=Journal+of+the+American+Chemical+Society&rft.au=Gordon%2C+Jesse+B&rft.au=Vilbert%2C+Avery+C&rft.au=Siegler%2C+Maxime+A&rft.au=Lancaster%2C+Kyle+M&rft.date=2019-02-27&rft.eissn=1520-5126&rft.volume=141&rft.issue=8&rft.spage=3641&rft_id=info:doi/10.1021%2Fjacs.8b13134&rft_id=info%3Apmid%2F30776222&rft_id=info%3Apmid%2F30776222&rft.externalDocID=30776222 |
| thumbnail_l | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/lc.gif&issn=1520-5126&client=summon |
| thumbnail_m | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/mc.gif&issn=1520-5126&client=summon |
| thumbnail_s | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/sc.gif&issn=1520-5126&client=summon |