The Chemistry of β-Diketiminatometal Complexes

Abstract

Contents 1. Introduction 3031 1.1. Definition of the β-Diketiminato Ligand and Scope of This Review 3031 1.2. Some Significant Developments 3032 2. Preparation of β-Diketimines and Their Metal Complexes 3034 2.1. Synthesis of a β-Diketimine from a β-Diketone or 1,1,3,3-Tetraalkoxypropane 3034 2.2. Synthesis of a Metal β-Diketiminate by Nitrile or Isonitrile Insertion into a Metal−Alkyl Bond 3034 2.3. Various Other Synthetic Routes to Metal β-Diketiminates 3035 2.4. Other Synthetic Routes to β-Diketimines 3035 3. Bonding Modes and Structural Features of β-Diketiminatometal Complexes 3037 4. Discussion of Specific β-Diketiminatometal Complexes 3039

Activation of Carbon−Hydrogen and Hydrogen−Hydrogen Bonds by Copper−Nitrenes: A Comparison of Density Functional Theory with Single- and Multireference Correlation Consistent Composite Approaches

“…[8][9][10][11][12][13][14] Ligands in the -diketiminate family have started to augment phosphines in the study of late TM catalysis. 15 Attention has also focused on -diketiminate and related ligands because of their ability to enforce low metal coordination numbers. Also, varying the substituents on the ligating nitrogens, the backbone carbons, linking the -diketiminate ring with other moieties to form fused rings, and so forth gives these ligands tunable electronic and steric features.…”

The Formazanate Ligand as an Electron Reservoir: Bis(Formazanate) Zinc Complexes Isolated in Three Redox States

“…[4] A class of ligands that has found widespread utility in the synthesis of metal complexes across the periodic table are the monoanionic β-diketiminates. [5] These are generally considered as stable ligand scaffolds without involvement in redox-chemistry. Recently, examples of β-diketiminate metal complexes were reported in which the ligand was either reduced to a metal-bound di-or trianion, [6] or oxidized to a neutral radical species.…”

Novel Syntheses of Symmetric Alkyl-substituted β-Diketimines with Dimethylsulfate Assisted by Microwave

“…Preparation of β-Ketoimine Ligands. CH 3 COCHC(NHCH(CH 3 ) 2 )CH 3 (1): Acetylacetone (5.00 g, 49.9 mmol) and isopropylamine (3.50 g, 59.9 mmol) was placed in a 100 mL round-bottom flask and the mixture was stirred at room temperature for 1 h. (2): Acetylacetone (5.00 g, 49.9 mmol) and tert-butylamine (4.40 g, 59.9 mmol) in 5 mL of ethanol was placed in a 100 mL round-bottom flask and the flask was sealed with a reflux condenser and placed into microwave cavity (CEM Co., Discover). When microwave was irradiated at a power of 150 W, the temperature was raised from room temperature to 130 o C. Once the predetermined temperature was reached, the reaction mixture was held at that temperature for 1 h. After cooling down to room temperature, the starting material and solvent were evaporated under vacuum and brown liquid was obtained (yield: 68.5%).…”