TY - JOUR
T1 - Aluminium amides derived from metallation of N,N′-di-tert-butyl-ethylenediamine
AU - Gardiner, Michael G.
AU - Lawrence, Stacey M.
AU - Raston, Colin L.
PY - 1996/11/21
Y1 - 1996/11/21
N2 - The metallation of N,N′-di-tert-butylethylenediamine by AlH3·NMe3 has been investigated and shown to proceed via the formation of the unstable secondary amine-stabilised amidoalane [AlH2(ButNCH2CH2NButH)]. This compound reacted with an additional equivalent of AlH3·NMe3 to yield the dibridging amidoalane complex [(AlH2)2{μ-N(But)CH2CH 2N(But)}] or a molecule of the diamine to give the triamidoaluminium species [Al(ButNCH2CH2NBut)(Bu tNCH2CH2NButH)]. In the absence of an excess of AlH3·NMe3 or N,N′-di-tert-butylethylenediamine, [AlH2(ButNCH2CH2NButH)] eliminates molecular hydrogen to give the trans isomer of the dimeric diamidoalane complex trans-[{AlH[μ-N(But)CH2CH2NBu t]}2] which is stable toward reaction with either of the reactants. A stable analogue of the intermediate [AlH2(ButNCH2CH2NButH)] was made by replacing a hydride by a chloride, achieved by using AlH2Cl·NMe3 as the metallating agent. The cis isomer of the dimeric diamidoalane cis-[AlH{[μ-N(But)CH2CH2NBu t]}2] was prepared from the unstable lithium diamido aluminium hydride species [{Li[N(But)CH2CH2NBut]AlH 2}n] via elimination of lithium hydride. The aluminium triamide and the cis and trans isomers of the dimeric aluminium diamide have been structurally authenticated.
AB - The metallation of N,N′-di-tert-butylethylenediamine by AlH3·NMe3 has been investigated and shown to proceed via the formation of the unstable secondary amine-stabilised amidoalane [AlH2(ButNCH2CH2NButH)]. This compound reacted with an additional equivalent of AlH3·NMe3 to yield the dibridging amidoalane complex [(AlH2)2{μ-N(But)CH2CH 2N(But)}] or a molecule of the diamine to give the triamidoaluminium species [Al(ButNCH2CH2NBut)(Bu tNCH2CH2NButH)]. In the absence of an excess of AlH3·NMe3 or N,N′-di-tert-butylethylenediamine, [AlH2(ButNCH2CH2NButH)] eliminates molecular hydrogen to give the trans isomer of the dimeric diamidoalane complex trans-[{AlH[μ-N(But)CH2CH2NBu t]}2] which is stable toward reaction with either of the reactants. A stable analogue of the intermediate [AlH2(ButNCH2CH2NButH)] was made by replacing a hydride by a chloride, achieved by using AlH2Cl·NMe3 as the metallating agent. The cis isomer of the dimeric diamidoalane cis-[AlH{[μ-N(But)CH2CH2NBu t]}2] was prepared from the unstable lithium diamido aluminium hydride species [{Li[N(But)CH2CH2NBut]AlH 2}n] via elimination of lithium hydride. The aluminium triamide and the cis and trans isomers of the dimeric aluminium diamide have been structurally authenticated.
UR - http://www.scopus.com/inward/record.url?scp=33748734390&partnerID=8YFLogxK
U2 - 10.1039/DT9960004163
DO - 10.1039/DT9960004163
M3 - Article
AN - SCOPUS:33748734390
SN - 0300-9246
SP - 4163
EP - 4169
JO - Journal of the Chemical Society. Dalton Transactions
JF - Journal of the Chemical Society. Dalton Transactions
IS - 22
ER -