%0 Journal Article
%A Felix, Ana M.
%A Dickie, Diane
A.
%A Horne, Ian S.
%A Page, Giang
%A Kemp, Richard A.
%D 2012
%T Addition of Aluminum and
Gallium Species to Aromatic
and Alkyl-Substituted 1,4-Diaza-1,3-butadiene Ligands
%U https://acs.figshare.com/articles/journal_contribution/Addition_of_Aluminum_and_Gallium_Species_to_Aromatic_and_Alkyl_Substituted_1_4_Diaza_1_3_butadiene_Ligands/2530849
%R 10.1021/ic202583w.s001
%2 https://acs.figshare.com/ndownloader/files/4173850
%K dicoordinated adduct
%K Al reactions
%K DiPPDAB ligand
%K aluminum reactions
%K chloride acceptors
%K methyl groups
%K Gallium Species
%K MeAlCl 2
%K rearrangement processes
%K methylated Al species
%K RDAB ligand
%K MeGaCl 2 act
%K Methylated Ga species
%K rearrangement reactions
%K GaCl 3
%K irreproducible results
%X In this report, we investigate the interactions of MexMCl3–x (x = 0–3, M = Al, Ga) with various aromatic
and alkyl-substituted
1,4-diaza-1,3-butadiene RDAB ligands (or α-diimine
ligands) to give a variety of structures in solution and in the solid
state. In combination with other previously reported structures, certain
general trends of reactivity of these species can be deduced, although
there are still some unexplained modes of reactivity. The methylated
Al species react with aromatic-substituted RDAB ligands
to provide final products that result from CN insertion into
the Al–CH3 group followed by rearrangement reactions.
The addition of methyl groups onto the backbone of the RDAB ligand is insufficient to stop the insertion and rearrangement
processes from occurring. In the case of MeAlCl2 with the
bulky DiPPDAB ligand, the reaction could be followed spectroscopically
from the monoadduct through the inserted/rearranged final product.
Methylated Ga species, however, are much less predictable in their
behavior with aromatic-substituted RDAB ligands. Depending
on the exact species and ratios used, coordinated adducts can be formed
and identified, or inserted/rearranged products similar to the aluminum
reactions can be obtained. Quite interestingly, cation/anion pairs
can also be formed in which GaCl3 or MeGaCl2 act as a chloride acceptors. This behavior was unique and substantially
different from the analogous Al reactions which formed either a dicoordinated
adduct or an inserted/rearranged complex. When the stronger-donating
alkyl-substituted RDAB ligands were used with Me2GaCl, only cation/anion pairs were obtained. Surprisingly, when the
same reactions were performed using Me2AlCl as a reagent,
irreproducible results were obtained.
%I ACS Publications