27661-80-9

Upstream product

• 116-14-3 polytetrafluoroethylene 
• 1295-35-8 bis(1,5-cyclooctadiene)nickel ⁽⁰⁾ 
• 74-85-1 ethene 
• 603-35-0 triphenylphosphine 

Relevant academic research and scientific papers

2,2,3,3-tetrafluoronickelacyclopentanes generated via the oxidative cyclization of tetrafluoroethylene and simple alkenes: A key intermediate in nickel-catalyzed C-C bond-forming reactions

Oxidative cyclization of tetrafluoroethylene (TFE) and ethylene with Ni(0) resulted in the formation of a five-membered nickelacycle. In the presence of PPh3 as an auxiliary ligand, the partially fluorinated five-membered nickelacycle was isolated and the structure was determined by X-ray analysis. This nickelacycle was found not only to react stoichiometrically with enones to give a cross-trimerization product but also to be a key reaction intermediate in the Ni(0)-catalyzed cotrimerization of TFE and ethylene, leading to 5,5,6,6-tetrafluoro-1-hexene.

Carbon-fluorine bond activation of tetrafluoroethylene on palladium(0) and nickel(0): Heat or lewis acidic additive promoted oxidative addition

The C-F bond cleavage reaction of tetrafluoroethylene (TFE; CF 2=CF2) with an M(0) complex (M = Pd, Ni) was investigated. The treatment of an M(0) precursor with TFE in the presence of the appropriate monodentate phosphine ligand led to a clean formation of the corresponding η2-TFE adduct (η2-TFE)M(PR3) 2. In the case of the Ni(0) species, in particular, the choice of phosphine ligands is crucial for the preparation of the desired η2-TFE complex: the use of either PCy3 or P iPr3 resulted in the target adduct, while less sterically hindered phosphines such as PPh3 and PnBu3 gave the known octafluoronickelacyclopentane as a result of the oxidative cyclization of two TFE molecules. Thermolysis of both palladium and nickel η2-TFE adducts bearing PCy3 as the ligand resulted in a C-F bond activation reaction and gave the corresponding (trifluorovinyl)metal fluorides, trans-(PCy3)2M(F)(CF=CF2). The reaction of (η2-TFE)Pd(PPh3)2 with LiI as an additive allowed cleavage of the C-F bond in THF, even at room temperature, and gave trans-(PPh3)2Pd(I)(CF=CF2) with a concomitant formation of lithium fluoride. Other metal halides, such as MgBr2 and AlCl3, also promoted the C-F bond cleavage of TFE. In addition, the use of either BF3·Et2O or B(C6F5)3 exerted a similar accelerative effect on the C-F bond activation of TFE on either nickel or palladium. The molecular structures of a series of η2-TFE and trifluorovinyl complexes were unambiguously determined by means of X-ray crystallography. The resultant (trifluorovinyl)palladium or -nickel species have shown the potential to utilize a key intermediate in cross-coupling reactions with organometallic reagents to prepare a variety of trifluorovinyl compounds.