Two-Coordinate Magnesium(I) Dimers Stabilized by Super Bulky Amido Ligands.
Identifieur interne : 003709 ( Ncbi/Curation ); 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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<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>
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