Stander-Grobler, Elzet Schuster, Oliver Heydenrych, Greta Cronje, Stephanie Tosh, Evangeline Albrecht, Martin Frenking, Gernot Raubenheimer, Helgard G. 2010-10-22 We report a thorough investigation of a series of isomeric complexes with the general formula <i>trans</i>-(pyridylidene)M(PPh₃)₂Cl (M = Pd, Ni). For the first time, a systematic comparison of <i>normal</i>, <i>abnormal</i>, and <i>remote</i> 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 <i>trans</i>-(pyridylidene)Pd(PPh₃)₂Cl as precursors in Suzuki−Miyaura-type cross-coupling suggests a correlation of <i>remote</i> bonding with catalyst robustness and effectivity. When metal precursors M(PPh₃)₄ are reacted with 2,4-dichloropyridinium salts, preferential formation of <i>remote</i> 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. application/pdf https://folia.unifr.ch/global/documents/301778 https://folia.unifr.ch/documents/301778/files/sch_pdn.pdf https://folia.unifr.ch/documents/301778/files/sch_pdn_sm.pdf https://folia.unifr.ch/documents/301778/files/sch_pdn_sm_cif.txt eng info:eu-repo/semantics/altIdentifier/doi/10.1021/om100431u info:eu-repo/semantics/openAccess License undefined Organometallics. - 2011, vol. 29, no. 22, p. 5821–5833 info:eu-repo/classification/udc/54 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) http://purl.org/coar/resource_type/c_6501