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Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Reactions of α-diimine-aluminum complexes with sodium alkynides: versatile structures of aluminum σ-alkynide
Yanxia Zhao1, Yanyan Liu, Biao Wu
1Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710069, China. yangxiaojuan@nwu.edu.cn.
Abstract:
Reaction of AlCl(3) with the monoanionic α-diimine ligand [NaL] yielded the complex [L˙(-)Al(III)Cl(2)(-)] (1, L = [(2,6-iPr(2)C(6)H(3))NC(Me)](2)), and subsequent reduction of by sodium metal afforded the mononuclear [L(2-)Al(III)Cl(-)(THF)] (2) and binuclear [L(2-)(THF)Al(II)-Al(II)(THF)L(2-)] (3). Compounds 2 and 3 exhibit interesting reactivities to sodium alkynides at room temperature. Treatment of dialumane 3 with 1 equiv. of 4-methylphenylacetylene in the presence of sodium metal yielded the asymmetric Al-Al-bonded compound [Na(Et(2)O)][LAl-Al(C[triple bond, length as m-dash]C(C(6)H(4)-Me))L] (4) containing an alkynyl group attached to one of the Al atoms. The reaction of 2 with 4-methylphenylacetylene and Na (or sodium 4-methylphenylacetylide) resulted in the mononuclear product [L(THF)Al(C[triple bond, length as m-dash]C-(C(6)H(4)-Me))] (5) containing a single terminal acetylide ligand. Precursor 2 reacted with 2 equiv. of phenylacetylene (or 4-methylphenylacetylene, trimethylsilylacetylene) and Na to give the tweezer "ate" complexes, [Na(THF)(DME)][LAl(C[triple bond, length as m-dash]CR)(2)] (R = C(6)H(5), ; C(6)H(4)-Me, ; Si(Me)(3), 6c), [Na(THF)](2)[LAl(C[triple bond, length as m-dash]CPh)(2)](2)(μ-C(7)H(8)) (7), [Na(C(7)H(8))][(μ-Na)][LAl(C[triple bond, length as m-dash]CSi(Me)(3))(2)](2) (8), as well as the polymeric [LAl(C[triple bond, length as m-dash]CPh)(2)Na](n) (9). In the products, two alkynyl groups coordinate terminally to one Al center and a sodium ion is embedded between these two alkynyls. Interestingly, both cycloaddition and terminal acetylide coordination of three equiv. of alkyne occurred in the reaction of with 1-hexyne, resulting in the unique dialuminum complex [Na(Et(2)O)](2)[{L(C(C(4)H(9))[double bond, length as m-dash]CH)}Al(C[triple bond, length as m-dash]C(C(4)H(9)))(2)](2) (10). Complexes 1-10 have been characterized by NMR ((1)H, (13)C) and IR spectroscopy, elemental analysis, and X-ray diffraction, and their electronic structures were studied by DFT calculations.
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