Collect. Czech. Chem. Commun. 2000, 65, 17-22

Nickel(0) and Palladium(0) Complexes with (Z,Z)-Ph2PCH2C(t-Bu)=N-N=C(t-Bu)CH2PPh2. Alkyne-to-Alkenyl Conversion in [Pd(MeOCOCCCOOMe){(Z,Z)-Ph2PCH2C(t-Bu)=N-N=C(t-Bu)CH2PPh2}]

Jan Čermáka,*, Stanislav Šabataa, Vratislav Blechtaa and Bernard L. Shawb

a Institute of Chemical Process Fundamentals, Academy of Sciences of the Czech Republic, 165 02 Prague, Czech Republic
b University of Leeds, Leeds LS2 9JT, United Kingdom


Novel zero-valent metal complexes [ML2{(Z,Z)-Ph2PCH2C(t-Bu)=N-N=C(t-Bu)CH2PPh2}] (M = Ni, L = CO, t-BuNC) with the azine diphosphine chelating in a nine-membered ring were prepared. The nickel dicarbonyl complex was found to be in an equilibrium with its isomer containing (E,Z)-chelated azine diphosphine, the equilibrium being on the side of the (Z,Z)-isomer below 60 °C. A similar palladium complex (M = Pd, L2 = CH3OCOC≡CCOOCH3) prepared earlier was found to undergo a rearrangement with simultaneous alkyne-to-alkenyl conversion of the acetylenedicarboxylate dimethyl ester ligand.

Keywords: Nickel; Palladium; Alkyne complexes; Chelates; P ligands; Phosphines; Azines; Bidentate ligands.

References: 11 live references.