Sterically encumbered aluminum aryloxide complexes

Jolin A. Jegier, David A. Atwood

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5 Scopus citations

Abstract

This work was conducted as-part of a broad-based effort to determine the factors that affect cation formation for organometallic aluminum complexes. Previous studies have shown that the cationic complexes [R2Al(NH2'Bu)2]X result from the combination of R2 AlX and excess NH2*Bu when X = Br and I. In the present study the effect of replacing one alkyl group with the relatively bulky aryloxide (2,6-di-ier<-butyl phenoxide = Ph'O) to yield complexes of formula [Me(Ph*O) A1X]2 (X = Cl (1), Br (2)) was examined. With excess NH2<Bu only the adduct species formed, Me(Ph*O)AlX(NH2'Bu) (where X = Cl (3), Br (4)). In using R2A1I a different type of reaction occurs and only Ph*OAlMe2(NH2*Bu) (5) and [NHs'Bu]I are obtained. Of related interest, the compound Me2(Ph*O)Al(THF) (6) is also reported. The presence of 4 as an adduct species indicates that the inductive effect of the aryloxide prevents cation formation where X = Br, in contrast to the complexes which possess only alkyl. All of the compounds were characterized by mp, 1H NMR, IR, elemental analyses, and in some cases, X-ray crystallography. X-ray data: (1) monoclinic, P21/n, a = 10.604(1), b - 20.776(4), c = 14.752(1) A, β = 92.450(1)°, V = 3247.1(7) A3, Z = 4, with 3245 reflections with F > 4.0 aF, R = 0.0436; (3) orthorhombic, Pno2i, a = 16.879(2), b = 12.315(2), c = 10.442(1) A, V = 2170.5(5) A3, Z = 4, with 1270 reflections with F > 4.0 aF, R = 0.0477; (5) orthorhombic, Pnali, a = 17.111(3), 6 = 12.375(1), c = 10.380(1) A, V = 2197.7(5) A3, Z = 4, with 1226 reflections with F > 4.0 aF, R = 0.0538. organometallic aluminum complex / [R2Al(NH2(Bu)2] / Me(Ph*O)AlX(NH2'Bu) / Ph*OAlMe2(NH2'Bu) / Me2(Ph*O)Al(THF) / aryloxy effect / X-ray analysis / JH NMR

Original languageEnglish
Pages (from-to)965-971
Number of pages7
JournalBulletin de la Societe Chimique de France
Volume133
Issue number10
StatePublished - 1996

ASJC Scopus subject areas

  • General Chemistry

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