ic961455l_si_001.pdf (385.57 kB)
Base Effects on the Formation of Four- and Five-Coordinate Cationic Aluminum Complexes
journal contribution
posted on 1997-05-07, 00:00 authored by Jolin A. Jegier, David A. AtwoodThis work was conducted as part of our continuing effort to
determine the factors that affect cation formation for
organometallic aluminum complexes. In this study, the interactions
of R2AlX (where R = Me, iBu,
tBu; X = Cl,
Br, I) with the monodentate bases thf, pyridine, NEt3,
HNiPr2,
H2NiBu,
H2NtBu, and OPPh3 are
examined to
determine the role of the base in cation formation. These
reactions resulted in the neutral adducts of the general
form R2AlX·base (1−6,
8, 10, and 12) as well as the cationic
complexes [R2Al(base)2]X
(7, 9, and 11). The
reactions of Me2AlX (where X = Cl, Br) with PMDETA
(N,N‘,N‘‘,N‘‘‘-pentamethyldiethylenetriamine)
and the
catalytic activity of the resulting cationic complexes (13
and 14) are also discussed. All of the compounds
were
characterized by mp, IR, 1H-NMR, and elemental analyses,
and in one an X-ray crystallographic study was carried
out. X-ray data for 13: triclinic,
P1̄, a = 6.9542(6) Å, b
= 12.2058(10) Å, c = 13.2417(11) Å, α =
106.236(2)°,
β = 98.885(2)°, γ = 93.807(2)°, V =
1059.06(15) Å3, and Z = 2 for 181
parameters refined on 4358 reflections
having F > 6.0σ(F), R =
0.0697, and Rw = 0.0697.