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6928576 
Journal Article 
The influence of halogen substituents on the course of hydrogallation and hydroalumination reactions 
Uhl, W; Claesener, M; Hepp, A; Jasper, B; Vinogradov, A; van Wüllen, L; Köster, TK; , 
2009 
Yes 
Dalton Transactions (Online)
ISSN: 1477-9234 
ROYAL SOC CHEMISTRY 
CAMBRIDGE 
10550-10562 
English 
20023879 
WOS:000272193900022 
Treatment of trimethylsilylethynylbenzene derivatives with HGaCl(2) afforded products, [C(6)H(6-x){C(H)=C(SiMe(3))GaCl(2)}(x)], in which by a very fast cis/trans-rearrangement the Ga and H atoms occupied opposite sides of the resulting C=C double bonds. The stability of the cis-forms considerably increased upon application of 1,3-dibromo- and pentafluorophenylalkyne derivatives. Two pairs of cis/trans-isomers could be characterized by crystal structure determinations and allow the direct comparison of structural parameters. For the first time an equilibrium was detected between cis- and trans-forms in solution. Treatment of 1,4-di(tert-butylalkynyl)benzene with HAlR(2) (R = CMe(3), CH(2)CMe(3)) afforded cyclophane-type molecules by the release of AlR(3). Only the neopentyl derivative could be isolated and characterized by crystal structure determination. In contrast, the dibromo compound, 1,4-Br(2)-2,5-(Me(3)CC[triple bond]C)(2)C(6)H(2), yielded the simple addition product, C(6)H(2)Br(2){C(AlR(2))=C(H)CMe(3)}(2) (R = CMe(3)). Condensation was hindered in this case by intramolecular Al-Br interactions. Surprisingly, the simple addition product was also isolated from the reaction of 1,4-(Me(3)CC[triple bond]C)(2)C(6)H(4) with the relatively small hydride HAlEt(2). Solid-state NMR spectra of the product revealed strong intermolecular Al-C interactions involving the negatively charged terminal vinylic carbon atoms, to give one-dimensional coordination polymers.