Reactions of α-diimine-aluminum complexes with sodium alkynides: versatile structures of aluminum σ-alkynide complexes.

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.