Two-Coordinate Magnesium(I) Dimers Stabilized by Super Bulky Amido Ligands.
Identifieur interne : 003709 ( Ncbi/Merge ); précédent : 003708; suivant : 003710Two-Coordinate Magnesium(I) Dimers Stabilized by Super Bulky Amido Ligands.
Auteurs : Aaron J. Boutland [Australie] ; Deepak Dange [Australie] ; Andreas Stasch [Australie] ; Laurent Maron [France] ; Cameron Jones [Australie]Source :
- Angewandte Chemie (International ed. in English) [ 1521-3773 ] ; 2016.
Abstract
A variety of very bulky amido magnesium iodide complexes, LMgI(solvent)0/1 and [LMg(μ-I)(solvent)0/1 ]2 (L=-N(Ar)(SiR3 ); Ar=C6 H2 {C(H)Ph2 }2 R'-2,6,4; R=Me, Pr(i) , Ph, or OBu(t) ; R'=Pr(i) or Me) have been prepared by three synthetic routes. Structurally characterized examples of these materials include the first unsolvated amido magnesium halide complexes, such as [LMg(μ-I)]2 (R=Me, R'=Pr(i) ). Reductions of several such complexes with KC8 in the absence of coordinating solvents have afforded the first two-coordinate magnesium(I) dimers, LMg-MgL (R=Me, Pr(i) or Ph; R'=Pr(i) , or Me), in low to good yields. Reductions of two of the precursor complexes in the presence of THF have given the related THF adduct complexes, L(THF)Mg-Mg(THF)L (R=Me; R'=Pr(i) ) and LMg-Mg(THF)L (R=Pr(i) ; R'=Me) in trace yields. The X-ray crystal structures of all magnesium(I) complexes were obtained. DFT calculations on the unsolvated examples reveal their Mg-Mg bonds to be covalent and of high s-character, while Ph⋅⋅⋅Mg bonding interactions in the compounds were found to be weak at best.
DOI: 10.1002/anie.201604362
PubMed: 27303934
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Boutland</name><affiliation wicri:level="1"><nlm:affiliation>School of Chemistry, Monash University, P.O. Box 23, Melbourne, VIC, 3800, Australia.</nlm:affiliation><country xml:lang="fr">Australie</country><wicri:regionArea>School of Chemistry, Monash University, P.O. Box 23, Melbourne, VIC, 3800</wicri:regionArea><wicri:noRegion>3800</wicri:noRegion></affiliation></author><author><name sortKey="Dange, Deepak" sort="Dange, Deepak" uniqKey="Dange D" first="Deepak" last="Dange">Deepak Dange</name><affiliation wicri:level="1"><nlm:affiliation>School of Chemistry, Monash University, P.O. Box 23, Melbourne, VIC, 3800, Australia.</nlm:affiliation><country xml:lang="fr">Australie</country><wicri:regionArea>School of Chemistry, Monash University, P.O. Box 23, Melbourne, VIC, 3800</wicri:regionArea><wicri:noRegion>3800</wicri:noRegion></affiliation></author><author><name sortKey="Stasch, Andreas" sort="Stasch, Andreas" uniqKey="Stasch A" first="Andreas" last="Stasch">Andreas Stasch</name><affiliation wicri:level="1"><nlm:affiliation>School of Chemistry, Monash University, P.O. Box 23, Melbourne, VIC, 3800, Australia.</nlm:affiliation><country xml:lang="fr">Australie</country><wicri:regionArea>School of Chemistry, Monash University, P.O. Box 23, Melbourne, VIC, 3800</wicri:regionArea><wicri:noRegion>3800</wicri:noRegion></affiliation></author><author><name sortKey="Maron, Laurent" sort="Maron, Laurent" uniqKey="Maron L" first="Laurent" last="Maron">Laurent Maron</name><affiliation wicri:level="3"><nlm:affiliation>Université de Toulouse et CNRS, INSA, UPS, UMR 5215, LPCNO, 135 Avenue de Rangueil, 31077, Toulouse, France. laurent.maron@irsamc.ups-tlse.fr.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Université de Toulouse et CNRS, INSA, UPS, UMR 5215, LPCNO, 135 Avenue de Rangueil, 31077, Toulouse</wicri:regionArea><placeName><settlement type="city">Toulouse</settlement><region type="region" nuts="2">Occitanie (région administrative)</region><region type="old region" nuts="2">Midi-Pyrénées</region></placeName></affiliation></author><author><name sortKey="Jones, Cameron" sort="Jones, Cameron" uniqKey="Jones C" first="Cameron" last="Jones">Cameron Jones</name><affiliation wicri:level="1"><nlm:affiliation>School of Chemistry, Monash University, P.O. Box 23, Melbourne, VIC, 3800, Australia. cameron.jones@monash.edu.</nlm:affiliation><country xml:lang="fr">Australie</country><wicri:regionArea>School of Chemistry, Monash University, P.O. Box 23, Melbourne, VIC, 3800</wicri:regionArea><wicri:noRegion>3800</wicri:noRegion></affiliation></author></analytic><series><title level="j">Angewandte Chemie (International ed. in English)</title><idno type="eISSN">1521-3773</idno><imprint><date when="2016" type="published">2016</date></imprint></series></biblStruct></sourceDesc></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">A variety of very bulky amido magnesium iodide complexes, LMgI(solvent)0/1 and [LMg(μ-I)(solvent)0/1 ]2 (L=-N(Ar)(SiR3 ); Ar=C6 H2 {C(H)Ph2 }2 R'-2,6,4; R=Me, Pr(i) , Ph, or OBu(t) ; R'=Pr(i) or Me) have been prepared by three synthetic routes. Structurally characterized examples of these materials include the first unsolvated amido magnesium halide complexes, such as [LMg(μ-I)]2 (R=Me, R'=Pr(i) ). Reductions of several such complexes with KC8 in the absence of coordinating solvents have afforded the first two-coordinate magnesium(I) dimers, LMg-MgL (R=Me, Pr(i) or Ph; R'=Pr(i) , or Me), in low to good yields. Reductions of two of the precursor complexes in the presence of THF have given the related THF adduct complexes, L(THF)Mg-Mg(THF)L (R=Me; R'=Pr(i) ) and LMg-Mg(THF)L (R=Pr(i) ; R'=Me) in trace yields. The X-ray crystal structures of all magnesium(I) complexes were obtained. DFT calculations on the unsolvated examples reveal their Mg-Mg bonds to be covalent and of high s-character, while Ph⋅⋅⋅Mg bonding interactions in the compounds were found to be weak at best.</div></front></TEI><pubmed><MedlineCitation Status="In-Data-Review" Owner="NLM"><PMID Version="1">27303934</PMID><DateCreated><Year>2016</Year><Month>07</Month><Day>29</Day></DateCreated><DateRevised><Year>2016</Year><Month>07</Month><Day>29</Day></DateRevised><Article PubModel="Print-Electronic"><Journal><ISSN IssnType="Electronic">1521-3773</ISSN><JournalIssue CitedMedium="Internet"><Volume>55</Volume><Issue>32</Issue><PubDate><Year>2016</Year><Month>Aug</Month><Day>01</Day></PubDate></JournalIssue><Title>Angewandte Chemie (International ed. in English)</Title><ISOAbbreviation>Angew. Chem. Int. Ed. Engl.</ISOAbbreviation></Journal><ArticleTitle>Two-Coordinate Magnesium(I) Dimers Stabilized by Super Bulky Amido Ligands.</ArticleTitle><Pagination><MedlinePgn>9239-43</MedlinePgn></Pagination><ELocationID EIdType="doi" ValidYN="Y">10.1002/anie.201604362</ELocationID><Abstract><AbstractText>A variety of very bulky amido magnesium iodide complexes, LMgI(solvent)0/1 and [LMg(μ-I)(solvent)0/1 ]2 (L=-N(Ar)(SiR3 ); Ar=C6 H2 {C(H)Ph2 }2 R'-2,6,4; R=Me, Pr(i) , Ph, or OBu(t) ; R'=Pr(i) or Me) have been prepared by three synthetic routes. Structurally characterized examples of these materials include the first unsolvated amido magnesium halide complexes, such as [LMg(μ-I)]2 (R=Me, R'=Pr(i) ). Reductions of several such complexes with KC8 in the absence of coordinating solvents have afforded the first two-coordinate magnesium(I) dimers, LMg-MgL (R=Me, Pr(i) or Ph; R'=Pr(i) , or Me), in low to good yields. Reductions of two of the precursor complexes in the presence of THF have given the related THF adduct complexes, L(THF)Mg-Mg(THF)L (R=Me; R'=Pr(i) ) and LMg-Mg(THF)L (R=Pr(i) ; R'=Me) in trace yields. The X-ray crystal structures of all magnesium(I) complexes were obtained. DFT calculations on the unsolvated examples reveal their Mg-Mg bonds to be covalent and of high s-character, while Ph⋅⋅⋅Mg bonding interactions in the compounds were found to be weak at best.</AbstractText><CopyrightInformation>© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.</CopyrightInformation></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Boutland</LastName><ForeName>Aaron J</ForeName><Initials>AJ</Initials><AffiliationInfo><Affiliation>School of Chemistry, Monash University, P.O. Box 23, Melbourne, VIC, 3800, Australia.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Dange</LastName><ForeName>Deepak</ForeName><Initials>D</Initials><AffiliationInfo><Affiliation>School of Chemistry, Monash University, P.O. Box 23, Melbourne, VIC, 3800, Australia.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Stasch</LastName><ForeName>Andreas</ForeName><Initials>A</Initials><AffiliationInfo><Affiliation>School of Chemistry, Monash University, P.O. Box 23, Melbourne, VIC, 3800, Australia.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Maron</LastName><ForeName>Laurent</ForeName><Initials>L</Initials><AffiliationInfo><Affiliation>Université de Toulouse et CNRS, INSA, UPS, UMR 5215, LPCNO, 135 Avenue de Rangueil, 31077, Toulouse, France. laurent.maron@irsamc.ups-tlse.fr.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Jones</LastName><ForeName>Cameron</ForeName><Initials>C</Initials><AffiliationInfo><Affiliation>School of Chemistry, Monash University, P.O. Box 23, Melbourne, VIC, 3800, Australia. cameron.jones@monash.edu.</Affiliation></AffiliationInfo></Author></AuthorList><Language>eng</Language><PublicationTypeList><PublicationType UI="D016428">Journal Article</PublicationType></PublicationTypeList><ArticleDate DateType="Electronic"><Year>2016</Year><Month>06</Month><Day>15</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">DFT calculations</Keyword><Keyword MajorTopicYN="N">bulky amides</Keyword><Keyword MajorTopicYN="N">magnesium(I)</Keyword><Keyword MajorTopicYN="N">metal-metal bonding</Keyword></KeywordList></MedlineCitation><PubmedData><History><PubMedPubDate PubStatus="received"><Year>2016</Year><Month>05</Month><Day>04</Day></PubMedPubDate><PubMedPubDate PubStatus="entrez"><Year>2016</Year><Month>6</Month><Day>16</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="pubmed"><Year>2016</Year><Month>6</Month><Day>16</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="medline"><Year>2016</Year><Month>6</Month><Day>16</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate></History><PublicationStatus>ppublish</PublicationStatus><ArticleIdList><ArticleId IdType="pubmed">27303934</ArticleId><ArticleId IdType="doi">10.1002/anie.201604362</ArticleId></ArticleIdList></PubmedData></pubmed><affiliations><list><country><li>Australie</li><li>France</li></country><region><li>Midi-Pyrénées</li><li>Occitanie (région administrative)</li></region><settlement><li>Toulouse</li></settlement></list><tree><country name="Australie"><noRegion><name sortKey="Boutland, Aaron J" sort="Boutland, Aaron J" uniqKey="Boutland A" first="Aaron J" last="Boutland">Aaron J. Boutland</name></noRegion><name sortKey="Dange, Deepak" sort="Dange, Deepak" uniqKey="Dange D" first="Deepak" last="Dange">Deepak Dange</name><name sortKey="Jones, Cameron" sort="Jones, Cameron" uniqKey="Jones C" first="Cameron" last="Jones">Cameron Jones</name><name sortKey="Stasch, Andreas" sort="Stasch, Andreas" uniqKey="Stasch A" first="Andreas" last="Stasch">Andreas Stasch</name></country><country name="France"><region name="Occitanie (région administrative)"><name sortKey="Maron, Laurent" sort="Maron, Laurent" uniqKey="Maron L" first="Laurent" last="Maron">Laurent Maron</name></region></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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