Ketiminate supported aluminum(III) complexes: Synthesis, characterization and reactivity

Synthesis and X‐ray Crystal Structures of β‐Ketoiminate Complexes

“…The side‐arm donor group (NMe 2 ) coordinates in all complexes to the Lewis‐acidic aluminum atom, resulting in the formation of five‐membered AlN 2 C 2 rings, and the Al–N bond lengths [2.2283(8) Å 7 , 2.1468(12) Å 12 , 2.0921(6) Å 13 , 2.1441(9) Å 14 ] are comparable to those reported for L1 Do2 Al(Me)Cl [2.252(2) Å] and L1 Do2 AlCl 2 [2.171(3) Å] . The axial Al–N2 bond lengths are significantly elongated compared to the equatorial Al–N1 bond lengths.…”

“…L1 Do1 AlMe 2 7 is a new polymorph of the known structure of L1 Do1 AlMe 2 and the bonding parameters (Al–O, Al–N, and Al–C bond length, endo ‐ and exo ‐cyclic bond angles) of both polymorphs are almost identical. In addition, the solid‐state structures of L1 Do1 Al(Cl)Me ( 12 ) and L1 Do1 AlCl 2 ( 13 ) are comparable to those of L1 Do2 Al(Me)Cl and L1 Do2 AlCl 2 , respectively, and their central Al–N [ 7 1.9857(7) Å; 12 1.9658(11) Å; 13 1.9414(6) Å; 14 1.9719(8) Å] and Al–O [ 7 1.8984(7) Å; 12 1.8541(11) Å; 13 1.8232(6) Å; 14 1.8656(7) Å] bond lengths and O–Al–N bond angles [ 7 88.65(3)°; 12 89.92(5)°; 13 91.15(3)°; 14 89.23(3)°] within the six‐membered AlONC 3 metallacycle also agree very well. The Al atoms in the complexes are fivefold coordinated and show distorted trigonal‐bipyramidal (tbp) coordination modes.…”

Synthesis and characterisation of novel aluminium and gallium precursors for chemical vapour deposition

“…1 This allows the precursor to be tailored to the specific CVD application. Metal b-ketoiminate precursors ranging from zinc, 27 group 13 [27][28][29][30] and, albeit unstable, group II metals 31 have been reported. A number of different R groups attached to the N donor atom have been explored and are mostly alkyl groups that increase the steric demand of the ligand, and donor functionalised groups, such as a polyether, which yield multidentate ligands.…”

Investigations into the structure, reactivity, and AACVD of aluminium and gallium amidoenoate complexes

“…Please do not adjust margins All Al-heteroatom bonds in 1-Al were found to be significantly shorter than the 5-coordinate complexes reported by Richards and Shulz previously, 40,41 which is likely a consequence of the comparatively electron deficient nature of the aluminum center in 1-Al. Complexes 2-Al and 3-Al both displayed a distorted trigonal bipyramidal geometry with a  4 value of 0.87 for 2-Al and 0.76 for 3-Al, suggesting that the Dip-substituted amidoeanote ligands in 3-Al distort the geometry of the aluminium center significantly more than the iPr-substituents in 2-Al.…”

“…Complex 1-Al represents the first example of a tetrahedral aluminium dichloride unit featuring a ligand that binds through both oxygen and nitrogen and was synthesised from the salt metathesis reaction of [Li(AME iPr )] and AlCl 3 (Scheme 1). Two previous examples of aluminium dichlorides featuring (O,N)-binding ligands have been reported by Richards 40 and Shulz, 41 with the formulae [AlCl 2 {(RNC(Me)CHC(Me)O}], R = Fig. 2 Previously reported zinc bis-amidoenoates (A and B), ethyl zinc amidoenoate dimers (C and D) and tungsten amidoenoate complexes (E and F).…”