Inhaltsübersicht.Lewis-Säure/Base-Addukte des Typs dmapϪMMe 3 (M ϭ Al 1, Ga 2, In 3, Tl 4) sowie dmapϪAlCl 3 (6) und dmapϪAl(t-Bu) 3 (7) wurden durch Reaktion von MR 3 mit 4-Dimethylaminopyridin (dmap) synthetisiert, während dmapϪAlH 3 (5) ausgehend von AlH 3 ·Et 2 O erhalten werden konnte. 1Ϫ7 wurden durch NMR-( 1 H, 13 C{ 1 H}) und Massenspektrometrie sowie mit-Abstract. Lewis acid-base adducts of the type dmapϪMMe 3 (M ϭ Al 1, Ga 2, In 3, Tl 4) as well as dmapϪAlCl 3 (6) and dmapϪAl(t-Bu) 3 (7) were synthesized by reaction of MR 3 with 4-dimethylamino-pyridine (dmap) whereas dmapϪAlH 3 (5) was obtained from AlH 3 ·Et 2 O. 1Ϫ7 were characterized by means of NMR ( 1 H, 13 C{ 1 H}) and mass spectrometry and elemental analysis. In addition, their solid state structures were determined by single * Priv.-Doz. Dr. S. Schulz
Reactions of an equimolar amount of 4-(dimethylamino)pyridine (dmap) with several Al−E heterocycles [R 2 AlE(SiMe 3 ) 2 ] x (E = P, As; R = Me, x = 3; R = Et, x = 2) and Ga−Sb heterocycles [R 2 GaSb(SiMe 3 ) 2 ] x (R = Me, x = 3; R = Et, x = 2) in hexane offers a general pathway for the formation of mono-
Reactions between low-valent [Cp*Al]4 and trialkylsilyl azides RR‘2SiN3 proceed with N2 elimination
and subsequent formation of iminoalanes [Cp*AlNSiRR‘2]
x
(R, R‘ = Et 1, i-Pr 2, t-Bu 3; R = t-Bu R‘
= Me 4), which further react with an equimolar amount of 4-(dimethylamino)pyridine (dmap) with
formation of dmap-stabilized iminoalanes of the general type [dmap-Al(Cp*)NSiRR‘2]2 (R, R‘ = Et 5,
i-Pr 6; R = t-Bu R‘ = Me 7). No reaction was observed for [Cp*AlNSi(t-Bu)3]2, 3. In contrast, Cp*Al
and RR‘2SiN3 react in the presence of dmap at elevated temperatures with C−H activation of the ortho-Hdmap and formation of dihydroanthracene-type compounds of the type [o-Al(Cp*)N(H)SiRR‘2-dmap]2
(R, R‘ = Et 8, i-Pr 9, t-Bu 10; R = t-Bu R‘ = Me 11). The reaction of Cp*Al and t-Bu3SiN3 with 2 equiv
of dmap proceeds with o-C−Hdmap activation of only one dmap molecule and formation of the dmap-stabilized monomeric aminoalane [o-Al(dmap)(Cp*)N(H)Si(t-Bu)3-dmap], 12. Compounds 3 and 5−12
were characterized by IR, mass, and multinuclear NMR spectroscopy (1H, 13C), and 3, 7, 8, 9, 11, and
12 also by single-crystal X-ray structure analysis.
Reactions between trialkylgallanes GaR 3 (R ) Me, Et, t-Bu) and triorganobismuthanes BiR′ 3 (R′ ) i-Pr, SiMe 3 ) lead to the formation of six Lewis acid-base adducts of the type R 3 Ga‚BiR′ 3 (Me 3 Ga‚Bi(SiMe 3 ) 3 , 1, Et 3 Ga‚Bi(SiMe 3 ) 3 , 2, t-Bu 3 Ga‚Bi(SiMe 3 ) 3 , 3, Me 3 Ga‚Bi(i-Pr) 3 , 4, Et 3 Ga‚Bi(i-Pr) 3 , 5, t-Bu 3 Ga‚Bi(i-Pr) 3 , 6). 2 and 6 are the first structurally characterized main group element-triorganobismuthane Lewis acid-base adducts. In addition, the synthesis and structural characterization of two Lewis base-stabilized, monomeric aluminum bismuthides of the type base-Al(R 2 )Bi(SiMe 3 ) 2 (base ) 4-(dimethylamino)pyridine (dmap); R ) Me 7, Et 8) is reported.
The heterocycles [{Me2AlE(SiMe3)2}x] (E=P–Bi) are powerful metathesis reagents in the presence of 4‐dimethylaminopyridine (dmap), thus allowing the synthesis of previously unknown Group 13/15 compounds. Reactions with [Me3Mdmap] (M=In, Tl) proceed with E(SiMe3)2 transfer to form the corresponding heterocycles [{Me2InBi(SiMe3)2}3] and [{Me2TlE(SiMe3)2}2] (E=P, As), which were characterized by NMR and MS analysis, and by single‐crystal X‐ray diffraction.
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