Facile hydrogen atom abstraction and sulfide formation in a methyl-thiolate capped iron-sulfur-carbonyl cluster.
Identifieur interne : 000127 ( Main/Exploration ); précédent : 000126; suivant : 000128Facile hydrogen atom abstraction and sulfide formation in a methyl-thiolate capped iron-sulfur-carbonyl cluster.
Auteurs : J Patrick Shupp [États-Unis] ; Michael J. RoseSource :
- Dalton transactions (Cambridge, England : 2003) [ 1477-9234 ] ; 2020.
Abstract
The interest in methyl group C-H bond activation near or bound to iron-containing clusters is of key biological importance, due to the broad relevance of radical SAM reactions. Specifically, such processes are implicated in the biogenesis of the interstitial carbide found in the nitrogenase FeMoco active site. In this work, we find that the diamagnetic, methyl-thiolate capped iron-carbonyl cluster anion [(CH3S)Fe3(CO)9]- (1) undergoes facile C-H hydrogen atom abstraction upon treatment with TEMPO. The process leads to (i) eradication of the CH3 moiety, (ii) formation of a sulfide bridge, and (iii) cluster dimerization-thereby generating the 'dimer of trimers' cluster [K(benzo-15-crown-5)2]2[(SFe2(CO)12)2Fe(CO)2] (2). In contrast, the corresponding isopropyl variant [Fe3(SiPr)(CO)9]- (3) does not react with TEMPO. Mass spectrometry confirmed the presence of TEMPOH, as well as CO oxidation vis a vis CO2 and 2,2,6,6-tetramethylpiperidine. GC-MS measurements of the headspace reveal that the ultimate fate of the methyl carbon is likely incorporation into multiple products-one of which may be a volatile low mass hydrocarbon-rather than carbon/carbide incorporation.
DOI: 10.1039/c9dt04098f
PubMed: 31802097
Affiliations:
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Rose</name></author></titleStmt><publicationStmt><idno type="wicri:source">PubMed</idno><date when="2020">2020</date><idno type="RBID">pubmed:31802097</idno><idno type="pmid">31802097</idno><idno type="doi">10.1039/c9dt04098f</idno><idno type="wicri:Area/Main/Corpus">000181</idno><idno type="wicri:explorRef" wicri:stream="Main" wicri:step="Corpus" wicri:corpus="PubMed">000181</idno><idno type="wicri:Area/Main/Curation">000181</idno><idno type="wicri:explorRef" wicri:stream="Main" wicri:step="Curation">000181</idno><idno type="wicri:Area/Main/Exploration">000181</idno></publicationStmt><sourceDesc><biblStruct><analytic><title xml:lang="en">Facile hydrogen atom abstraction and sulfide formation in a methyl-thiolate capped iron-sulfur-carbonyl cluster.</title><author><name sortKey="Shupp, J Patrick" sort="Shupp, J Patrick" uniqKey="Shupp J" first="J Patrick" last="Shupp">J Patrick Shupp</name><affiliation wicri:level="4"><nlm:affiliation>The University of Texas at Austin, Austin, TX 78758, USA. mrose@cm.utexas.edu.</nlm:affiliation><country xml:lang="fr">États-Unis</country><wicri:regionArea>The University of Texas at Austin, Austin, TX 78758</wicri:regionArea><placeName><region type="state">Texas</region><settlement type="city">Austin (Texas)</settlement></placeName><orgName type="university">Université du Texas à Austin</orgName></affiliation></author><author><name sortKey="Rose, Michael J" sort="Rose, Michael J" uniqKey="Rose M" first="Michael J" last="Rose">Michael J. Rose</name></author></analytic><series><title level="j">Dalton transactions (Cambridge, England : 2003)</title><idno type="eISSN">1477-9234</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">The interest in methyl group C-H bond activation near or bound to iron-containing clusters is of key biological importance, due to the broad relevance of radical SAM reactions. Specifically, such processes are implicated in the biogenesis of the interstitial carbide found in the nitrogenase FeMoco active site. In this work, we find that the diamagnetic, methyl-thiolate capped iron-carbonyl cluster anion [(CH<sub>3</sub>S)Fe<sub>3</sub>(CO)<sub>9</sub>]<sup>-</sup> (1) undergoes facile C-H hydrogen atom abstraction upon treatment with TEMPO. The process leads to (i) eradication of the CH<sub>3</sub> moiety, (ii) formation of a sulfide bridge, and (iii) cluster dimerization-thereby generating the 'dimer of trimers' cluster [K(benzo-15-crown-5)<sub>2</sub>]<sub>2</sub>[(SFe<sub>2</sub>(CO)<sub>12</sub>)<sub>2</sub>Fe(CO)<sub>2</sub>] (2). In contrast, the corresponding isopropyl variant [Fe<sub>3</sub>(S<sup>i</sup>Pr)(CO)<sub>9</sub>]<sup>-</sup> (3) does not react with TEMPO. Mass spectrometry confirmed the presence of TEMPOH, as well as CO oxidation vis a vis CO<sub>2</sub> and 2,2,6,6-tetramethylpiperidine. GC-MS measurements of the headspace reveal that the ultimate fate of the methyl carbon is likely incorporation into multiple products-one of which may be a volatile low mass hydrocarbon-rather than carbon/carbide incorporation.</div></front></TEI><pubmed><MedlineCitation Status="PubMed-not-MEDLINE" Owner="NLM"><PMID Version="1">31802097</PMID><DateCompleted><Year>2019</Year><Month>12</Month><Day>17</Day></DateCompleted><DateRevised><Year>2019</Year><Month>12</Month><Day>20</Day></DateRevised><Article PubModel="Print-Electronic"><Journal><ISSN IssnType="Electronic">1477-9234</ISSN><JournalIssue CitedMedium="Internet"><Volume>49</Volume><Issue>1</Issue><PubDate><Year>2020</Year><Month>Jan</Month><Day>07</Day></PubDate></JournalIssue><Title>Dalton transactions (Cambridge, England : 2003)</Title><ISOAbbreviation>Dalton Trans</ISOAbbreviation></Journal><ArticleTitle>Facile hydrogen atom abstraction and sulfide formation in a methyl-thiolate capped iron-sulfur-carbonyl cluster.</ArticleTitle><Pagination><MedlinePgn>23-26</MedlinePgn></Pagination><ELocationID EIdType="doi" ValidYN="Y">10.1039/c9dt04098f</ELocationID><Abstract><AbstractText>The interest in methyl group C-H bond activation near or bound to iron-containing clusters is of key biological importance, due to the broad relevance of radical SAM reactions. Specifically, such processes are implicated in the biogenesis of the interstitial carbide found in the nitrogenase FeMoco active site. In this work, we find that the diamagnetic, methyl-thiolate capped iron-carbonyl cluster anion [(CH<sub>3</sub>S)Fe<sub>3</sub>(CO)<sub>9</sub>]<sup>-</sup> (1) undergoes facile C-H hydrogen atom abstraction upon treatment with TEMPO. The process leads to (i) eradication of the CH<sub>3</sub> moiety, (ii) formation of a sulfide bridge, and (iii) cluster dimerization-thereby generating the 'dimer of trimers' cluster [K(benzo-15-crown-5)<sub>2</sub>]<sub>2</sub>[(SFe<sub>2</sub>(CO)<sub>12</sub>)<sub>2</sub>Fe(CO)<sub>2</sub>] (2). In contrast, the corresponding isopropyl variant [Fe<sub>3</sub>(S<sup>i</sup>Pr)(CO)<sub>9</sub>]<sup>-</sup> (3) does not react with TEMPO. Mass spectrometry confirmed the presence of TEMPOH, as well as CO oxidation vis a vis CO<sub>2</sub> and 2,2,6,6-tetramethylpiperidine. GC-MS measurements of the headspace reveal that the ultimate fate of the methyl carbon is likely incorporation into multiple products-one of which may be a volatile low mass hydrocarbon-rather than carbon/carbide incorporation.</AbstractText></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Shupp</LastName><ForeName>J Patrick</ForeName><Initials>JP</Initials><Suffix></Suffix><AffiliationInfo><Affiliation>The University of Texas at Austin, Austin, TX 78758, USA. mrose@cm.utexas.edu.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Rose</LastName><ForeName>Michael J</ForeName><Initials>MJ</Initials><Suffix></Suffix></Author></AuthorList><Language>eng</Language><PublicationTypeList><PublicationType UI="D016428">Journal Article</PublicationType></PublicationTypeList><ArticleDate DateType="Electronic"><Year>2019</Year><Month>12</Month><Day>05</Day></ArticleDate></Article><MedlineJournalInfo><Country>England</Country><MedlineTA>Dalton Trans</MedlineTA><NlmUniqueID>101176026</NlmUniqueID><ISSNLinking>1477-9226</ISSNLinking></MedlineJournalInfo><CitationSubset>IM</CitationSubset></MedlineCitation><PubmedData><History><PubMedPubDate PubStatus="pubmed"><Year>2019</Year><Month>12</Month><Day>6</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="medline"><Year>2019</Year><Month>12</Month><Day>6</Day><Hour>6</Hour><Minute>1</Minute></PubMedPubDate><PubMedPubDate PubStatus="entrez"><Year>2019</Year><Month>12</Month><Day>6</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate></History><PublicationStatus>ppublish</PublicationStatus><ArticleIdList><ArticleId IdType="pubmed">31802097</ArticleId><ArticleId IdType="doi">10.1039/c9dt04098f</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><noCountry><name sortKey="Rose, Michael J" sort="Rose, Michael J" uniqKey="Rose M" first="Michael J" last="Rose">Michael J. Rose</name></noCountry><country name="États-Unis"><region name="Texas"><name sortKey="Shupp, J Patrick" sort="Shupp, J Patrick" uniqKey="Shupp J" first="J Patrick" last="Shupp">J Patrick Shupp</name></region></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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