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}]

Čermák, Jan; Šabata, Stanislav; Blechta, Vratislav; Shaw, Bernard L.

doi:10.1135/cccc20000017

CCCC > Archive > 2000, Volume 65 > Issue 1 > p. 17

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 Čermák^a,*, Stanislav Šabata^a, Vratislav Blechta^a and Bernard L. Shaw^b

^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

Abstract

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.

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