화학공학소재연구정보센터
Inorganic Chemistry, Vol.58, No.11, 7545-7553, 2019
Stereoelectronic Profiling of Expanded-Ring N-Heterocyclic Carbenes
Heterobis(carbene) complexes of palladium(II) and gold(I) containing expanded-ring N-heterocyclic carbenes (erNHCs) have been prepared in order to study their electronic properties. erNHCs with mesityl substituents were found to exhibit anisotropic interferences, which hampered ranking of their donicities by C-13 NMR spectroscopy. The anisotropy effects were found to be stronger in the linear gold complexes, where a smaller coordination number allows the wingtips to spread out more. erNHCs with flexible N-benzyl groups are more suitable, and their donor strengths were found to gradually increase from five- to seven-membered heterocycles. The same trend can also be obtained by comparing the (1)J(C-H) coupling constants of the respective salts, although significant differences between seven- and eight-membered erNHCs could not be detected. The %V-bur values of erNHCs obtained from structures of their palladium and gold complexes revealed that the anisotropic interferences increase with overall steric bulk.