Faculté des sciences

Pyridine-derived N-heterocyclic carbenes: an experimental and theoretical evaluation of the bonding in and reactivity of selected normal and abnormal complexes of nickel(II) and palladium(II)

Stander-Grobler, Elzet ; Schuster, Oliver ; Heydenrych, Greta ; Cronje, Stephanie ; Tosh, Evangeline ; Albrecht, Martin ; Frenking, Gernot ; Raubenheimer, Helgard G.

In: Organometallics, 2011, vol. 29, no. 22, p. 5821–5833

We report a thorough investigation of a series of isomeric complexes with the general formula trans-(pyridylidene)M(PPh₃)₂Cl (M = Pd, Ni). For the first time, a systematic comparison of normal, abnormal, and remote bonding modes is presented. X-ray structural and ¹³C NMR data indicate the importance of carbenoid mesomeric contributions in their compound class.... Plus

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    Summary
    We report a thorough investigation of a series of isomeric complexes with the general formula trans-(pyridylidene)M(PPh₃)₂Cl (M = Pd, Ni). For the first time, a systematic comparison of normal, abnormal, and remote bonding modes is presented. X-ray structural and ¹³C NMR data indicate the importance of carbenoid mesomeric contributions in their compound class. The catalytic performance of the palladium complexes trans-(pyridylidene)Pd(PPh₃)₂Cl as precursors in Suzuki−Miyaura-type cross-coupling suggests a correlation of remote bonding with catalyst robustness and effectivity. When metal precursors M(PPh₃)₄ are reacted with 2,4-dichloropyridinium salts, preferential formation of remote carbene complexes occurs and indications are that electronic parameters rather than steric influences are responsible for the observed selectivity. Calculations at the BP86/TZ2P level of theory support interpretation of the results.