TY - JOUR
T1 - Reactions of α-diimine-aluminum complexes with sodium alkynides
T2 - versatile structures of aluminum σ-alkynide complexes
AU - Zhao, Yanxia
AU - Liu, Yanyan
AU - Wu, Biao
AU - Yang, Xiao Juan
N1 - Publisher Copyright:
© The Royal Society of Chemistry.
PY - 2015/8/14
Y1 - 2015/8/14
N2 - Reaction of AlCl3 with the monoanionic α-diimine ligand [NaL] yielded the complex [L•-AlIIICl2-] (1, L = [(2,6-iPr2C6H3)NC(Me)]2), and subsequent reduction of 1 by sodium metal afforded the mononuclear [L2-AlIIICl-(THF)] (2) and binuclear [L2-(THF)AlII-AlII(THF)L2-] (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(Et2O)][LAl-Al(C≡C(C6H4-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≡C-(C6H4-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≡CR)2] (R = C6H5, 6a; C6H4-Me, 6b; Si(Me)3, 6c), [Na(THF)]2[LAl(C≡CPh)2]2(μ-C7H8) (7), [Na(C7H8)][(μ-Na)][LAl(C≡CSi(Me)3)2]2 (8), as well as the polymeric [LAl(C≡CPh)2Na]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 2 with 1-hexyne, resulting in the unique dialuminum complex [Na(Et2O)]2[{L(C(C4H9)=CH)}Al(C≡C(C4H9))2]2 (10). Complexes 1-10 have been characterized by NMR (1H, 13C) and IR spectroscopy, elemental analysis, and X-ray diffraction, and their electronic structures were studied by DFT calculations.
AB - Reaction of AlCl3 with the monoanionic α-diimine ligand [NaL] yielded the complex [L•-AlIIICl2-] (1, L = [(2,6-iPr2C6H3)NC(Me)]2), and subsequent reduction of 1 by sodium metal afforded the mononuclear [L2-AlIIICl-(THF)] (2) and binuclear [L2-(THF)AlII-AlII(THF)L2-] (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(Et2O)][LAl-Al(C≡C(C6H4-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≡C-(C6H4-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≡CR)2] (R = C6H5, 6a; C6H4-Me, 6b; Si(Me)3, 6c), [Na(THF)]2[LAl(C≡CPh)2]2(μ-C7H8) (7), [Na(C7H8)][(μ-Na)][LAl(C≡CSi(Me)3)2]2 (8), as well as the polymeric [LAl(C≡CPh)2Na]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 2 with 1-hexyne, resulting in the unique dialuminum complex [Na(Et2O)]2[{L(C(C4H9)=CH)}Al(C≡C(C4H9))2]2 (10). Complexes 1-10 have been characterized by NMR (1H, 13C) and IR spectroscopy, elemental analysis, and X-ray diffraction, and their electronic structures were studied by DFT calculations.
UR - http://www.scopus.com/inward/record.url?scp=84937485276&partnerID=8YFLogxK
U2 - 10.1039/c5dt01693b
DO - 10.1039/c5dt01693b
M3 - Article
AN - SCOPUS:84937485276
SN - 1477-9226
VL - 44
SP - 13671
EP - 13680
JO - Dalton Transactions
JF - Dalton Transactions
IS - 30
ER -