Synthesis, characterisation and catalytic activity of Pd(II) and Ni(II) complexes with new cyclic α-diphenylphosphino-ketoimines. Crystal structure of 2,6-diisopropyl- N-(2-diphenylphosphino-cyclopentylidene)aniline and of 2,6-diisopropyl- N-(2-diphenylphosphino-cyclohexylidene)aniline

• Published in: Journal of organometallic chemistry 2002-11, Vol.662 (1), p.150-171
• Main Authors: Keim, Wilhelm, Killat, Stefan, Nobile, Cosimo F, Suranna, Gian Paolo, Englert, Ulli, Wang, Ruimin, Mecking, Stefan, Schröder, Dirk Lucas
• Format: Article
• Language: English
• Subjects: Ethylene oligomerisation; Methyl complexes; Nickel; Palladium; Phosphino ketoimines
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/S0022-328X(02)01903-4

New cyclic α-diphenylphosphino-ketoimines have been synthesised by deprotonation of the corresponding imine and subsequent reaction with chlorodiphenylphosphine. The crystal structures of two of these compounds containing a cyclopentylidene and cyclohexylidene backbone are discussed. Reaction of these bidentate phosphorus–nitrogen (P ∧N) ligands with (cod)Pd(CH 3)Cl leads to neutral complexes of the general formula (P ∧N)Pd(CH 3)Cl which have been reacted with AgSbF 6 to yield cationic complexes of formula [(P ∧N)Pd(CH 3)(NCCH 3)]SbF 6. Reaction of these ligands with (1,2-dimethoxyethane)NiBr 2 yields neutral nickel(II) complexes that have been characterised by IR and elemental analysis. Cationic Pd(II) complexes as well as MAO-activated neutral nickel(II) complexes have been used as ethylene oligomerisation catalysts. The cationic palladium(II) complexes show a marked pressure dependence of TOF, with α-olefin fraction and Schulz-Flory α-values explainable in the light of the accepted mechanism for analogous complexes. By increasing the steric bulkiness of the substituent on the imine, or by using ligands with cyclohexylidene or cycloheptylidene backbone instead of cyclopentylidene, a drop in catalytic activity is observed. Nickel(II) complexes of the title ligands activated with MAO permit to confirm the latter conclusions. In comparison with palladium their use brings to comparable linearities but higher oligomerisation grades as well as α-olefin fraction. Cationic palladium(II) complexes are also active in the propene and 1-butene oligomerisation. Neutral complexes of new α-(diphenylphosphino)-ketoimines have been obtained by cyclooctadiene displacement from (cod)Pd(CH 3)(Cl). Reaction of the neutral complexes with AgSbF 6 yielded the corresponding cationic complexes. Neutral Ni(II) complexes have been obtained by reaction with (1,2-dimethoxyethane)NiBr 2. Cationic Pd(II) complexes and MAO-activated neutral Ni(II) complexes are active olefin oligomerisation catalysts.