Allyl‐Aluminium Compounds

Abstract

The preparation of aluminium derivatives containing allyl or methallyl groups is reported. Their reactivity and physical properties are discussed.

Formation and Reactivity of 1,3‐Dialuminium Alkanes

“…In fact, the presence simultaneously of the three products, their ratio (see h g . ) , and the extent of their deuteration, seem to indicate that they originate from 7 and 8 according to equations (3) and (4), and that a 1 +-3 shift of aluminium atoms with elimination of olefin occurs easily even at room temperature: (3) (4) As expected, at higher temperature the whole process is accelerated, but a number of collateral reactions occur as well, and the results appear much more complicated.…”

“…Materials. The preparation of 1 and 2 is described in a previous paper [4]. Commercial diethylaluminium hydride (I< & K Laboratories) was used without further purification.…”

“…Their existence, however, was demonstrated in the auto-addition products of allyl-aluminium derivatives [2] and in the hydro-alumination products of allene [2] and of hex-1-en-5-yne [3]. To obtain more information on the chemical properties of this type of compounds we attempted their synthesis through auto-addition of methallyl-diethyl-aluminium (1) and hydro-aluminium of 1 and of the stable methallyl-dimethyl-aluminium ( 2 ) iecently prepared [4]. No pure 1,3-dialuminium compounds could be isolated, but their existence in solution was proved, and some aspects of their thermal decomposition and of their reactivity have been investigated.…”

“…At the same time the formation of increasing amounts of different hydrocarbons was noticed after hydrolysis. To obtain a better understanding of these decompositions, the solvolysis was carried out with Q-d,-methanol, and the positions, previously bound to alumi- 2,4,4, 2,4,4,6, Mono-and tri-deuterated olefins were present in minor amounts (-10% each). nium, labelled by deuterium in each hydrocarbon, were determined by mass spectroscopy.…”

The behaviour of β-triketimine cobalt complexes in the polymerization of isoprene

“…In neither case was there any clear relationship between [Al] and M n . 52 Both of these factors in concert make it likely that any bridging between Co and Al would be likely to occur via chloride, rather than via polymeryl, and so reduce the opportunity for chain transfer to Al to occur. This is in stark contrast to most group 4 cases, where strong dependence of M n on [Al] is normally found, 48 as also with lanthanides and isoprene, 49 and also even on our own results with closely similar Co complexes with butadiene where M n decreased as [Al] increased, 36 though these, as for most group 4 and lanthanide work, used MAO or R 3 Al rather than DEAC.…”