“…Notably, the Im-C 6 H 4 X angle (see Tables 3 and S11†) gradually increases while going from unsubstituted 3 (25.8(5)–50.72(5)°) through m -/ p -substituted 3b , 3e , 3k , 3i , 3l (39.14(5)–45.60(5)°) and o -F 3a 26 (50.55(7)–63.02(5)°) to o -Cl/Br/CF 3 3d , 3g and 3j (64.32(10)–67.53(6)°). Since sterically hindered Pd/NHC complexes of types Hal 2 Pd(1,3-(2,6-R 2 C 6 H 4 ) 2 Im) 2 and [HalPd(1,3-(2,6-R 2 C 6 H 4 ) 2 Im)] 2 (μ-Hal) 2 exhibit Im-C 6 H 4 X dihedral angle values of up to 90° (see the CSD, ver.…”