Two-Coordinate Magnesium(I) Dimers Stabilized by Super Bulky Amido Ligands.
Identifieur interne : 001493 ( Main/Exploration ); précédent : 001492; suivant : 001494Two-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
Affiliations:
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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><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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