Single-Step Insertion of Sulfides and Thiolate into Iron Carbide-Carbonyl Clusters: Unlocking the Synthetic Door to FeMoco Analogues.
Identifieur interne : 000042 ( Main/Exploration ); précédent : 000041; suivant : 000043Single-Step Insertion of Sulfides and Thiolate into Iron Carbide-Carbonyl Clusters: Unlocking the Synthetic Door to FeMoco Analogues.
Auteurs : Chris Joseph [États-Unis] ; Caitlyn R. Cobb [États-Unis] ; Michael Rose [États-Unis]Source :
- Angewandte Chemie (International ed. in English) [ 1521-3773 ] ; 2020.
Abstract
We report the one-step syntheses, X-ray structures, and spectroscopic characterization of synthetic iron clusters bearing inorganic sulfides or thiolate with interstitial carbide motifs. Treatment of historical iron-carbide-carbonyl clusters [Fe n ( μ n -C)(CO) m ] x ( n = 5,6; m = 15,16; x = 0,-2) with electrophilic sulfur sources (S 2 Cl 2 , S 8 ) results in the formation of several μ 4 -S 'dimers of clusters' ( 1 and 2 ), and moreover the iron-sulfide-(sulfocarbide) clusters 3 and 4 . The core 'carbide' motif in 3 and 4 is the sulfocarbide unit {C-S} 4- , which serves as a structural model for the proposed intermediate in the radical-SAM biogenesis of the M-cluster. Furthermore, the 'electrophilic sulfur' strategy has been extended to provide the first ever thiolato-iron-carbide complex: An analogous reaction with toluylsulfenyl-chloride (tolS-Cl) affords the cluster [Fe 5 ( μ 5 -C)(SC 7 H 7 )(CO) 13 ] - ( 5 ). The 'electrophilic sulfur donor' strategy described herein provides a breakthrough towards developing logical syntheses of biomimetic iron-sulfur-carbide clusters like FeMoco.
DOI: 10.1002/anie.202011517
PubMed: 33089646
Affiliations:
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Cobb</name><affiliation wicri:level="4"><nlm:affiliation>University of Texas at Austin, Chemistry, UNITED STATES.</nlm:affiliation><country xml:lang="fr" wicri:curation="lc">États-Unis</country><wicri:regionArea>University of Texas at Austin, Chemistry</wicri:regionArea><orgName type="university">Université du Texas à Austin</orgName><placeName><settlement type="city">Austin (Texas)</settlement><region type="state">Texas</region></placeName></affiliation></author><author><name sortKey="Rose, Michael" sort="Rose, Michael" uniqKey="Rose M" first="Michael" last="Rose">Michael Rose</name><affiliation wicri:level="4"><nlm:affiliation>The University of Texas at Austin, Chemistry, 105 E 24th St, Stop A5300, 78712, Austin, UNITED STATES.</nlm:affiliation><country xml:lang="fr" wicri:curation="lc">États-Unis</country><wicri:regionArea>The University of Texas at Austin, Chemistry, 105 E 24th St, Stop A5300, 78712, Austin</wicri:regionArea><orgName type="university">Université du Texas à Austin</orgName><placeName><settlement type="city">Austin (Texas)</settlement><region type="state">Texas</region></placeName></affiliation></author></analytic><series><title level="j">Angewandte Chemie (International ed. in English)</title><idno type="eISSN">1521-3773</idno><imprint><date when="2020" type="published">2020</date></imprint></series></biblStruct></sourceDesc></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">We report the one-step syntheses, X-ray structures, and spectroscopic characterization of synthetic iron clusters bearing inorganic sulfides or thiolate with interstitial carbide motifs. Treatment of historical iron-carbide-carbonyl clusters [Fe n ( μ n -C)(CO) m ] x ( n = 5,6; m = 15,16; x = 0,-2) with electrophilic sulfur sources (S 2 Cl 2 , S 8 ) results in the formation of several μ 4 -S 'dimers of clusters' ( 1 and 2 ), and moreover the iron-sulfide-(sulfocarbide) clusters 3 and 4 . The core 'carbide' motif in 3 and 4 is the sulfocarbide unit {C-S} 4- , which serves as a structural model for the proposed intermediate in the radical-SAM biogenesis of the M-cluster. Furthermore, the 'electrophilic sulfur' strategy has been extended to provide the first ever thiolato-iron-carbide complex: An analogous reaction with toluylsulfenyl-chloride (tolS-Cl) affords the cluster [Fe 5 ( μ 5 -C)(SC 7 H 7 )(CO) 13 ] - ( 5 ). The 'electrophilic sulfur donor' strategy described herein provides a breakthrough towards developing logical syntheses of biomimetic iron-sulfur-carbide clusters like FeMoco.</div></front></TEI><pubmed><MedlineCitation Status="Publisher" Owner="NLM"><PMID Version="1">33089646</PMID><DateRevised><Year>2020</Year><Month>10</Month><Day>22</Day></DateRevised><Article PubModel="Print-Electronic"><Journal><ISSN IssnType="Electronic">1521-3773</ISSN><JournalIssue CitedMedium="Internet"><PubDate><Year>2020</Year><Month>Oct</Month><Day>22</Day></PubDate></JournalIssue><Title>Angewandte Chemie (International ed. in English)</Title><ISOAbbreviation>Angew Chem Int Ed Engl</ISOAbbreviation></Journal><ArticleTitle>Single-Step Insertion of Sulfides and Thiolate into Iron Carbide-Carbonyl Clusters: Unlocking the Synthetic Door to FeMoco Analogues.</ArticleTitle><ELocationID EIdType="doi" ValidYN="Y">10.1002/anie.202011517</ELocationID><Abstract><AbstractText>We report the one-step syntheses, X-ray structures, and spectroscopic characterization of synthetic iron clusters bearing inorganic sulfides or thiolate with interstitial carbide motifs. Treatment of historical iron-carbide-carbonyl clusters [Fe n ( μ n -C)(CO) m ] x ( n = 5,6; m = 15,16; x = 0,-2) with electrophilic sulfur sources (S 2 Cl 2 , S 8 ) results in the formation of several μ 4 -S 'dimers of clusters' ( 1 and 2 ), and moreover the iron-sulfide-(sulfocarbide) clusters 3 and 4 . The core 'carbide' motif in 3 and 4 is the sulfocarbide unit {C-S} 4- , which serves as a structural model for the proposed intermediate in the radical-SAM biogenesis of the M-cluster. Furthermore, the 'electrophilic sulfur' strategy has been extended to provide the first ever thiolato-iron-carbide complex: An analogous reaction with toluylsulfenyl-chloride (tolS-Cl) affords the cluster [Fe 5 ( μ 5 -C)(SC 7 H 7 )(CO) 13 ] - ( 5 ). The 'electrophilic sulfur donor' strategy described herein provides a breakthrough towards developing logical syntheses of biomimetic iron-sulfur-carbide clusters like FeMoco.</AbstractText><CopyrightInformation>© 2020 Wiley-VCH GmbH.</CopyrightInformation></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Joseph</LastName><ForeName>Chris</ForeName><Initials>C</Initials><AffiliationInfo><Affiliation>University of Texas at Austin, Chemistry, UNITED STATES.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Cobb</LastName><ForeName>Caitlyn R</ForeName><Initials>CR</Initials><AffiliationInfo><Affiliation>University of Texas at Austin, Chemistry, UNITED STATES.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Rose</LastName><ForeName>Michael</ForeName><Initials>M</Initials><AffiliationInfo><Affiliation>The University of Texas at Austin, Chemistry, 105 E 24th St, Stop A5300, 78712, Austin, UNITED STATES.</Affiliation></AffiliationInfo></Author></AuthorList><Language>eng</Language><PublicationTypeList><PublicationType UI="D016428">Journal Article</PublicationType></PublicationTypeList><ArticleDate DateType="Electronic"><Year>2020</Year><Month>10</Month><Day>22</Day></ArticleDate></Article><MedlineJournalInfo><Country>Germany</Country><MedlineTA>Angew Chem Int Ed Engl</MedlineTA><NlmUniqueID>0370543</NlmUniqueID><ISSNLinking>1433-7851</ISSNLinking></MedlineJournalInfo><CitationSubset>IM</CitationSubset><KeywordList Owner="NOTNLM"><Keyword MajorTopicYN="N">FeMoco</Keyword><Keyword MajorTopicYN="N">biogenesis</Keyword><Keyword MajorTopicYN="N">biomimetic</Keyword><Keyword MajorTopicYN="N">carbide</Keyword><Keyword MajorTopicYN="N">nitrogenase</Keyword></KeywordList></MedlineCitation><PubmedData><History><PubMedPubDate PubStatus="received"><Year>2020</Year><Month>08</Month><Day>22</Day></PubMedPubDate><PubMedPubDate PubStatus="accepted"><Year>2020</Year><Month>10</Month><Day>20</Day></PubMedPubDate><PubMedPubDate PubStatus="revised"><Year>2020</Year><Month>10</Month><Day>09</Day></PubMedPubDate><PubMedPubDate PubStatus="entrez"><Year>2020</Year><Month>10</Month><Day>22</Day><Hour>5</Hour><Minute>45</Minute></PubMedPubDate><PubMedPubDate PubStatus="pubmed"><Year>2020</Year><Month>10</Month><Day>23</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="medline"><Year>2020</Year><Month>10</Month><Day>23</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate></History><PublicationStatus>aheadofprint</PublicationStatus><ArticleIdList><ArticleId IdType="pubmed">33089646</ArticleId><ArticleId IdType="doi">10.1002/anie.202011517</ArticleId></ArticleIdList></PubmedData></pubmed><affiliations><list><country><li>États-Unis</li></country><region><li>Texas</li></region><settlement><li>Austin (Texas)</li></settlement><orgName><li>Université du Texas à Austin</li></orgName></list><tree><country name="États-Unis"><region name="Texas"><name sortKey="Joseph, Chris" sort="Joseph, Chris" uniqKey="Joseph C" first="Chris" last="Joseph">Chris Joseph</name></region><name sortKey="Cobb, Caitlyn R" sort="Cobb, Caitlyn R" uniqKey="Cobb C" first="Caitlyn R" last="Cobb">Caitlyn R. 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