Synthesis, Characterization, and Reaction of Aluminum Halide Amides Supported by a Bulky β-Diketiminato Ligand

Abstract

Monomeric aluminum chloride amides with the general formula LAl(Cl)NR 2 (1, R ) Me; 2, R ) iPr; 3, R ) SiMe 3 ; L ) HC[C(Me)N(Ar)] 2 ; Ar ) 2,6-iPr 2 C 6 H 3 ) were prepared by selected routes. Treatment of LAlBr 2 (4) and LAlI 2 with LiNMe 2 yielded LAl(Br)NMe 2 (5) and LAl(I)NMe 2 (6), respectively. The alkylation of 1 and 2 with MeLi gave the corresponding methylated compounds LAl(Me)NR 2 (7, R ) Me; 8, R ) iPr); however, no reaction of 3 with MeLi was observed because of steric hindrance. Subsequent fluorination of 1-3 afforded LAl(F)NR 2 (9, R ) Me; 10, R ) iPr; 11, R ) SiMe 3 ). Compounds 1-11 were characterized by multinuclear NMR, electron impact mass spectrometry, and IR. The constitution of compounds 1-3 was confirmed by single-crystal X-ray diffraction studies.

A New Entry into Aluminum Chemistry: [L1AlMe]⋅THF, a Versatile Building Block for Bimetallic and Polymetallic Complexes

“…. [11] The methyl protons of the AlMe group resonate as a singlet (d = À0.97 ppm) in the spectrum and the resonance shows a downfield shift compared with that of 1.…”

“…Bimetallic complex 4 is produced in good yield as a red solid, and is soluble in toluene, THF, benzene, and diethyl ether. (14), Al3ÀCl1 2.1661(7), Al3ÀC59 1.9510(17), Ge1ÀN1 2.0350(13), Ge1ÀN2 2.0442(13), Ge1ÀC34 2.0945(16), C34ÀC33 1.484(2); N3-Al3-N4 97.93(6), Cl1-Al1-C59 110.60(6), N1-Ge1-N2 90.66(5), Ge1-C34-C33 107.28 (11). Non-coordinate n-hexane molecules and all hydrogen atoms have been omitted for clarity.…”

Preparation and Reactivity Studies of Four and Five coordinated Amidinate Aluminum Compounds

“…It is worthy to mention that our group earlier reported the use of Me 3 SnF as the fluorinating agent to synthesis compounds containing AlÀ F bond. [32][33][34] The concentrated toluene solution of 4 at À 32°C afforded the colorless single crystals. Refluxing (X=Cl, Br) in diethyl ether and n-hexane mixture.…”

The role of the bis-trimethylsilylamido ligand, [N{SiMe3}2]−, in main group chemistry. Part 2: Structural chemistry of the metallic p-block elements

“…Other simple molecular species containing the Al-N{SiMe 3 } 2 unit have been reported in the last 10-15 years, including Al(BDI Ar )(N{SiMe 3 } 2 )Cl (3) [13], an example with the acyclic tetradentate Schiff base derived from bis-5,5 -(1,3-ethanediyldiimino)-2,2-dimethyl-4-hexene-3-one (4) [14], and the bimetallic methylene bridged bis-amide, H 2 C{Al(N{SiMe 3 } 2 ) 2 } 2 (5) [15]. Aluminium hydrides are important reagents in synthetic chemistry and a number of reports of compounds containing Al-H groups in combination with the bis-trimethylsilylamido ligand have been reported.…”