Alumino‐organic derivatives of some dioximes

Abstract

The alumino-organic combinations of the dioximes (DOxH 2 ) examined in this paper result from the substitution of the hydrogen bonds of oximes by alumino-organic groups. Relative to the same alumino-organic derivatives, diphenylglyoxime (DPGH 2 ) behaves similarly to dimethylglyoxime (DMGH 2 ). The chemical reactivity of DPGH 2 towards these alumino-organic compounds is, however, less than in the case of DMGH 2 . An exception is the monomer state of (DPG)[Al(i-C 4 H 9 ) 2 ] 2 in benzene solution. The behavior relative to amines of alkyl derivatives is similar to that found in coordinated oximes. In contrast, phenylaluminum derivatives of DMGH 2 and DPGH 2 are not soluble in amines. All compounds reported in this paper were separated from the reaction mixture as colored powders and were characterized by chemical analyses, IR spectroscopy, X-ray diffraction spectra and 1 H NMR. Finally, a comparison between the reactivity of free and coordinated dioximes is briefly considered. It is hoped that such comparisons will throw light on the problems associated with the reactivity of free and coordinated oxides versus alumino-organic compounds.

Synthesis, structural and optical properties of novel borylated Cu(II) and Co(II) metal complexes of 4-benzylaminobiphenylglyoxime

“…In the complexes, broad bands in the 3448-3429 cm À1 range may be assigned to m(H 2 O) of coordinated water molecules [16]. These vibration data are in agreement with those previously reported for borylated metal complexes [6][7][8]17,18].…”

“…Experiments on the reactivity of cobalt(II) and copper(II) dimethylglyoximates with boron, aluminium and zinc compounds have resulted in a new class of compounds corresponding to the formula given in Fig. 1 [8,9]. The possibility of an apical modification of vicdioximes is stipulated by the relative availability of functionalized boron-containing Lewis acids as efficient capping agents.…”

“Isomerism” of Coordination Modes and Numbers in Pentanuclear Organozinc Hydroxylamides: An Exercise in Subtle Substituent Size Effects

“…In metal alkoxide/aryloxide chemistry, [1] an increase in aggregate dimensionality is already well established [compare the Al 2 O 2 ring {(Me 2 Al)[O(2,6-iPr 2 -C 6 H 3 )]} 2 [2] with the "double cube" [(MeZn) 3 (OMe) 4 ] 2 Zn [3] (CN = 4, 6)]. [4] The highly diverse chemistry of the O-N double-donor array (hydroxylamines or oximes) provides a plethora of aggregation motifs, for example in group 13 complexes, [5][6][7][8][9] and ought to be transferable to zinc for the exploration of similar extensions {compare the six-membered ring dimer [(Me 2 Al)(ON=CMe 2 )] 2 [5a,5b] with the tetrahedroid oximate [(MeZn)(ON=CMe 2 )] 4 [10] (CN = 4)}.…”

Organoaluminium complexes with sterically demanding oximato ligands: does a bulky and rigid ligand backbone change the aggregation motif?

“…9 This shows that neither the size of the metal complex fragment, nor the higher inductive donation of electron density from the two tert-butyl substituents has a considerable influence. Furthermore, organoaluminium dimethylglyoximates were also shown to exhibit the above motif (two Al 2 N 2 O 2 rings linked by two ligands), 10 underlining that the aggregation preferences are not altered when a flexible skeleton is employed.…”