Two Types of Intramolecular Addition of an Al−N Multiple-Bonded Monomer LAlNAr‘ Arising from the Reaction of LAl with N₃Ar‘ (L = HC[(CMe)(NAr)]₂, Ar‘ = 2,6-Ar₂C₆H₃, Ar = 2,6-iPr₂C₆H₃)

Abstract

The reaction of beta-diketiminated aluminum(I) monomer LAl with a large bulky azide N3Ar' (L = HC(CMeNAr)2, Ar' = 2,6-Ar2C6H3, Ar = 2,6-iPr2C6H3) in the temperature range from -78 degrees C to room temperature affords two different isomers 2 and 3, which have been characterized by spectroscopic and X-ray structural analyses, as well as elemental analysis. The variable-temperature 1H NMR kinetic studies of this reaction indicate the existence of the monomer LAlNAr' (1) at low temperature and the thermal stability of the compounds increases in the order of 1 < 2 < 3.

On the non-innocence of “Nacnacs”: ligand-based reactivity in β-diketiminate supported coordination compounds

“…The most striking feature of this structure, shown on Fig. 59,296 Similarly, our group isolated a metallacyclobutane amido species from the reaction of (MAD)Nb(vNar)(N t Bu)(OEt 2 ) with t BuN 3 , the formation of which is explained by a two-step process involving (a) nitrene transfer and reformation of an dissymmetric BDI ligand leading the Nb(III) imido (BDI (Dipp,tBu),Me )Nb (NDipp) intermediate species (see section 4) and (b) imidomediated C-H bond activation of the t Bu group from the asymmetric BDI ligand (Scheme 84bottom). 292 Note that upon substitution by arylchloride groups, intramolecular ortho chlorine coordination appears to be necessary to stabilize the cationic molybdenum imido alkylidene species (Scheme 82).…”

Reactions of Fluoroalkenes with an Aluminium(I) Complex

“…[20][21][22] We,a nd others,h ave previously shown that the monomeric Al I reagent 1 reacts with C À Fb onds of fluoroalkanes and fluoroarenes; [23,24] herein, we describe the reaction of 1 with industrially relevant fluoroalkenes.This reactivity is an example of agrowing number of approaches in which alowvalent main-group metal mimics the redox behaviour of at ransition metal. [24][25][26][27][28][29][30] As part of this analysis we have isolated an unprecedented aluminium metallocyclopropane complex and show that the reaction of an alkene with 1 is reversible.…”

Reactivity Studies of LAlH2 [L = HC(CMeNAr)2, Ar = 2, 6‐iPr2C6H3] with 2‐[(2‐Hydroxybenzylidene)amino]‐3‐mercapto­propionic Acid and Benzene‐1, 2‐diamine

“…Compound 3 exhibits a band at ν = 3374 cm -1 , which is quite close to those (ν = 3398 cm -1 and ν = 3220 cm -1 ) reported for N-H stretching frequencies. [13,14] Compounds 2 ( Figure 1) and 3 ( Figure 2) crystallize in the orthorhombic space group P2 1 2 1 2 1 and Cmca, respectively. [15] which should be attributed to the ring tension.…”