230950-98-8

Upstream product

• 15133-82-1 tetrakis(triphenylphosphine)nickel⁽⁰⁾ 
• 109-63-7 trifluoroborane diethyl ether 

Downstream Products

• 15245-43-9 tris(triphenylphosphine)nickel(I) bromide 

Relevant academic research and scientific papers

Influence of alcohols on the formation of the nickel complexes active in ethene oligomerization in the catalytic system Ni(PPh3) 4/BF3·OEt2

The influence of ethanol and selected other alcohols on the formation of active nickel complexes for ethylene oligomerization was studied for the Ni(PPh3)4/BF3·OEt2 system by EPR and 1H NMR spectroscopy. Both the presence of Ni(I) complexes and Ni(II) hydrides could be established. Coordinatively unsaturated Ni(I) complexes were shown to be the active catalysts for ethylene oligomerization, whereas the Ni(II) hydrides were shown to be inactive. The alcohol act as a promoter for the Ni(PPh3)4/BF3·OEt 2 by facilitating the formation of the active Ni(I) complexes.

Cationic complexes of monovalent nickel as catalysts for styrene polymerization

The interaction of the [Ni(PPh3)3]BF4 complex with styrene and the products of styrene conversion in the polymerization reaction were studied by EPR and 13C NMR spectroscopy. The structure of the σ-carbocationic complex of Ni(I) formed by the interaction of styrene with the [Ni(PPh3)3]BF4 cationic phosphine complex of Ni(I) was characterized in detail. It was found that the reaction of styrene polymerization occurred with the participation of the coordination center of the σ-carbocationic complex (coordination catalysis), whereas the reaction of telomerization occurred with the participation of the cationic center of this complex (ionic catalysis). The resulting polymer contained active terminal double bonds; it is a promising macromonomer for the synthesis of grafted copolymers. The discovered capacity of alcohols to undergo nucleophilic addition to a growing polymer chain offers strong possibilities for preparing functional polymers and block copolymers.

The EPR study of the promotion effect of alcohols on the (PPh3)4Ni + BF3 · OEt2 catalytic system

To develop notions on the mechanism of the promoting effect of alcohols on the (PPh3)4Ni + nBF3 · OEt2 catalytic system, the reactions between the individual Ni(I) alkoxyl complexes and boron trifluoride etherate were studied by the EPR method, as were the processes running in the catalytic system in situ during its promotion. It was shown that during the interaction of the Ni(I) alkoxyl complexes with the boron trifluoride etherate, the alkoxyl acidoligands are exchanged for the fluoride anion and the phosphine ligands are slightly eliminated from the coordination sphere of Ni(I). Alcohols introduced into the catalytic system undergo dehydration. The promoting effect of the alcohol in the catalytic system reduces to the facilitation of the phosphine ligand elimination, which is due to the formation of the Ni(I) alkoxy complexes and the generation of the Ni-R(H) active particles as a result of the insertion of the unsaturated hydrocarbon molecules along the Ni-OR bond.