Methyl(2-phosphanylphenolato[P,O])nickel(II) Complexes – Synthesis, Structure, and Activity as Ethene Oligomerization Catalysts

Reactions of various substituted 2-phosphanylphenols 1a–f with half-molar amounts of cis-[MeNi(μ-OMe)(PMe3)]2 have been found to yield square-planar methyl(2-phosphanylphenolato)(trimethylphosphane)nickel(II) complexes 2a–f. 2JPP coupling constants of 305–316 Hz at low temperature indicate a trans-configuration for the products, while broad 31P-NMR signals at room temperature can be attributed to rapid dissociation of PMe3. Reaction with excess 1 gave rigid bis(2-phosphanylphenolato)nickel(II) complexes as exemplified by 3e, whereas addition of PMe3 to 2a led to the pentacoordinate methyl(2-phosphanylphenolato)bis(trimethylphosphane)nickel(II) complex 4a. Higher yields of 4a and 4d were obtained by reactions of 1a and 1d with Me2Ni(PMe3)3. Single-crystal X-ray diffraction analyses of 3e and 4a have revealed the structures as square-planar trans-bis- and trigonal-bipyramidal mono(2-phosphanylphenolato)nickel(II) P1O-chelate complexes, respectively. The methylnickel complexes 2 and 4 have been found to be effective one-component catalysts for the oligomerization of ethene. High conversions (> 96%) were achieved with the P-basic derivatives 2e, 2f, and 4d bearing one or two branched alkyl groups (isopropyl, tert-butyl), whereas the diphenylphosphanyl derivatives were less active; 4d gave shorter oligomers than 2e or 2f.