181707-20-0

Upstream product

• 49673-40-7 N,N'-bis(2,6-dimethylphenyl)butane-2,3-diimine 
• 87-62-7 2,6-dimethylaniline 

Downstream Products

• 264907-31-5 (2,6-Me₂C₆H₃NC(Me)C(Me)N-2,6-Me₂C₆H₃)Pd(Me)(NCMe)(+)*SbF₆(-) 

Relevant academic research and scientific papers

Switching the Reactivity of Palladium Diimines with “Ancillary” Ligand to Select between Olefin Polymerization, Branching Regulation, or Olefin Isomerization

Coordinating solvents are commonly employed as ancillary ligands to stabilize late transition metal complexes and are conventionally considered to have little effect on the reaction products. Our work identifies that the presence of ancillary ligand in Pd-diimine catalyzed polymerizations of α-olefins can drastically alter reactivity. The addition of different amounts of acetonitrile allows for switching between distinct reaction modes: isomerization–polymerization with high branching (0 equiv.), regular chain-walking polymerization (1 equiv.), and alkene isomerization with no polymerization (>20 equiv.). Optimization of the isomerization reaction mode led to a general set of conditions to switch a wide variety of diimine complexes into efficient alkene isomerization catalysts, with catalyst loading as low as 0.005 mol %.

Unexpected formation of [(Me2-Xyl-DAB)Pd(η3-6- methyloct-2-en-1- id)][SbF6] (Me2-Xyl-DAB = 2,3-dimethyl-1,4-bis(2,6-dimethylphenyl)- diazabuta-1,3-diene)

Reaction of [(COD)Pd(Me)Cl] with Ag[SbF6] and 1.5 eq of the N N Me2-Xyl-DAB (2,3-dimethyl-N,N0- bis(2,6-dimethylphenyl)-diazabuta-1, 3-dien) afforded the title complex [(Me2-Xyl-DAB) Pd(η3-6-methylcyclooct- 2-en-1-id)][SbF6]. From a single crystal XRD study, 1H NMR and MS it is clear, that the compound contains a cationic Pd(II) complex with a neutral diaza-butadiene chelate ligand and an anionic, thus allylic, η3-6-methyl- cyclooct-2-en-1-id coligand. Presumably, the cationic complex has been formed by methylation of one of the olefin groups of the coordinated COD ligand. Details of this very interesting reaction were discussed in view of much related observations.