METALLACYCLEN AUS CO2 UND DIMETHYLBUTADIEN AM KOMPLEXRUMPF (L)Ni0: STRRUKTUR UND REAKTIVITAET ALS FUNKTION DER NEUTRALLIGANDEN L

Article abstract of DOI:10.1016/0022-328X(85)87239-9

Cyclo-(L)-Ni(CH22C(CH3)C(CH3)CH2COO can be synthesized either by the oxidative coupling of CO2 and diene at t he complex moiety (L)Ni, or by the exchange of neutral ligands in metallacycle I (L=N,N'-tetramethylene diamine (TMED)).X-Ray analyses of the compounds with L=Ph3P and Cy3P show that the C5O chains are bonded similarly, with an η³-allyl- and a monodentate carboxylato group at the ends of the chains.Thermal investigations and reactions with ?-acceptor ligands were carried out as a function of the neutral ligands L.The reaction of I with ?-acidic 1,4-diazadienes leads to 3,4-dimethyl-penta(2,4)dienecarboxylic acid and simulat es a partial step of a possible catalytic cycle: oxidative coupling - reductive elimination under H-shift.