Organoaluminum Silylamido Complexes

Abstract

The reaction between [Et2AlCl] and 1 equiv of HN(SiMe3)2 in CH2Cl2 afforded colorless crystals of [Et2AlCl{NH(SiMe3)2}] (1). In contrast, reaction of [Et2AlCl] with 1 equiv of HN(SiMe2H)2 or HN t Bu(SiMe3) resulted in the isolation of dimers, of the type [EtAlCl{NH(R‘)}]2 (2, R‘ = SiMe2H; 3, R‘ = t Bu). Reaction of [Et3Al] with 1 equiv of HN(SiMe2H)2 or HN(SiMe3)2 yielded the expected dimeric complexes, [Et2Al{N(SiMe2H)2}]2 (4) and [Et2Al{N(SiMe3)2}]2 (5), via ethane elimination. The related reaction between [MeAlCl2] and HN t Bu(SiMe3) in CH2Cl2 solution resulted in the formation of the 1:1 adduct [MeAlCl2{NH2( t Bu)}] (6). The structures of compounds 1 and 6 have been determined by X-ray crystallography. In addition, the decomposition of 1 and 6 has been studied by thermal gravimetric analysis.

Group 13 and 14 Alkyl Derivatives of the Imido−Nitrido Metalloligand [{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)]

“…The Al−N distance of 1.902(2) Å is shorter than those found in 9 (average 1.981(6) Å) but similar to that found in [MeCl 2 Al{N(SnMe 3 ) 3 }], 1.919(8) Å . The Al−N, Al−C (1.977(3) Å), and Al−Cl (average 2.174(1) Å) bond lengths in 13 compare well with those recently reported for [MeCl 2 Al(NH 2 t Bu)] . The sum of angles M−N(23)−M (329.8°) is very close to an ideal tetrahedral geometry.…”

Intramolecularly Stabilized o-Carboranyl Aluminum Complexes: Synthesis, Characterization, and X-ray Structural Studies

“…The Al(1)-N(1) distance in 3 (2.039(1) Å) was longer than that obtained in the corresponding amine-ligated aryl system [o-(Me 2 NCH 2 )C 6 H 4 ]AlBr 2 (2.003(5) Å). 7 The Al(1)-N(1) distance of 2.039(1) Å was in agreement with the corresponding values observed in the adducts formed between AlX 3 and NR 3 [43][44][45][46][47][48][49][50]; all distances were longer than the sum of the covalent radii for aluminum and nitrogen (1.95 Å) [51]. The Al(1)-C(1) distance (1.938(1) Å) was similar to that reported for other organoaluminum compounds [6,7,[52][53][54][55].…”

Intramolecularly Stabilized o-Carboranyl Aluminum Complexes: Synthesis, Characterization, and X-ray Structural Studies

“…The Al(1)-N(1) distance in 3 (2.039(1) Å) is longer than that in the corresponding amine-ligated aryl system [o-(Me2NCH2)C6H4]AlBr2 (2.003(5) Å). 7 The Al(1)-N(1) distance of 2.039(1) Å is in agreement with the corresponding values observed in adducts formed between X3Al and NR3; [19][20][21][22][23][24][25][26] all distances are longer than the sum of the covalent radii for aluminum and nitrogen (1.95 Å). 27 The Al(1)-C(1) distance (1.938(1) Å) is similar to that reported for other organoaluminum compounds.…”