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)

We report a thorough investigation of a series of isomeric complexes with the general formula trans -(pyridylidene)M(PPh 3 ) 2 Cl (M = Pd, Ni). For the first time, a systematic comparison of normal, abnormal, and remote bonding modes is presented. X-ray structural and 13 C NMR data indicate the importance of carbenoid mesomeric contributions in their compound class. The catalytic performance of the palladium complexes trans -(pyridylidene)Pd(PPh 3 ) 2 Cl as precursors in Suzuki−Miyaura-type cross-coupling suggests a correlation of remote bonding with catalyst robustness and effectivity. When metal precursors M(PPh 3 ) 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.