Nickel and iron complexes with N,P,N-type ligands: synthesis, structure and catalytic oligomerization of ethylene

The N,P,N-type ligands bis(2-picolyl)phenylphosphine (), bis(4,5-dihydro-2-oxazolylmethyl)phenylphosphine (), bis(4,4-dimethyl-2-oxazolylmethyl)phenylphosphine () and bis(2-picolyloxy)phenylphosphine () were used to synthesize the corresponding pentacoordinated Ni(ii) complexes Ni{bis(2-picolyl)phenylphosphine}Cl(2)] (), Ni{bis(4,5-dihydro-2-oxazolylmethyl)phenylphosphine}Cl(2)] (), Ni{bis(4,4-dimethyl-2-oxazolylmethyl)phenylphosphine}Cl(2)] () and Ni{bis(2-picolyloxy)phenylphosphine}Cl(2)] (), respectively. The hexacoordinated iron complexes Fe{bis(2-picolyl)phenylphosphine}(2)]Cl(3)FeOFeCl(3)] (), Fe{bis(4,5-dihydro-2-oxazolylmethyl)phenylphosphine}(2)]Cl(3)FeOFeCl(3)] () and the tetracoordinated complex Fe{bis(4,4-dimethyl-2-oxazolylmethyl)phenylphosphine}Cl(2)] (abbreviated FeCl(2)(NPN(Me2)-N,N)]) were prepared by reaction of FeCl(2).4H(2)O with ligands , respectively. The crystal structures of the octahedral complexes and , determined by X-ray diffraction, showed that two tridentate ligands are facially coordinated to the metal centre with a cis-arrangement of the P atoms and the dianion (mu-oxo)bistrichloroferrate(iii)] compensates the doubly positive charge of the complex. The cyclic voltammograms of and showed two reversible redox couples attributed to the reduction of the dianion (Fe(2)OCl(6))(2-) (-0.24 V for and -0.20 V for vs. SCE) and to the oxidation of the Fe(ii) ion of the complex (0.67 V for and 0.52 V for vs. SCE). The cyclic voltammogram of FeCl(2)(NPN(Me2)-N,N)] showed a reversible redox couple at -0.17 V vs. SCE assigned to the oxidation of the Fe(ii) atom and an irreversible process at 0.65 V. The complexes , and FeCl(2)(NPN(Me2)-N,N)] have been evaluated in the catalytic oligomerization of ethylene with AlEtCl(2) or MAO as cocatalyst. The nickel complex proved to be the most active precatalyst in the series, with a turnover frequency (TOF) of 61 800 mol(C(2)H(4)) mol(Ni)(-1) h(-1) with 10 equiv. of AlEtCl(2) and 12 200 mol(C(2)H(4)) mol(Ni)(-1) h(-1) with 200 equiv. of MAO. Precatalysts and were the most selective in butenes, up to 90% with 6 equiv. of AlEtCl(2) and 89% with 2 equiv. of AlEtCl(2), respectively, and up to 92% butenes with 400 equiv. of MAO and 91% butenes with 200 equiv. MAO, respectively. The best selectivities for 1-butene were provided by and AlEtCl(2) (up to 31% with 6 equiv.) and with MAO (up to 72% with 200 equiv.). The iron complexes were not significantly active with AlEtCl(2) or MAO as cocatalyst.