Pyramidalization/twisting of the amide functional group via remote steric congestion triggered by metal coordination† †Electronic supplementary information (ESI) available. CCDC 1494998–1495005. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc03669d Click here for additional data file. Click here for additional data file.

3-1. 1a–Pd Complexes 8 3-1-1. Detailed NMR of 1a for peak assignments 8 3-1-2. Detailed NMR of 1a/Pd for peak assignments 10 3-1-3. Detailed NMR of (1a)2/Pd for peak assignments 13 3-1-4. Stacked 1H and 13C NMR of 1a, 1a/Pd, and (1a)2/Pd 17 3-2. 1b–Pd Complex 19 3-2-1. Detailed NMR of 1b for peak assignments 19 3-2-2. Detailed NMR of (1b)2/Pd for peak assignments 23 3-2-3. Stacked 1H and 13C NMR of 1b and (1b)2/Pd 30 3-1. 1c–Pd Complex 31 3-3-1. Detailed NMR of 1c for peak assignments 31 3-3-2. Detailed NMR of (1c)2/Pd for peak assignments 34 3-3-3. Stacked 1H and 13C NMR of 1c and (1c)2/Pd 44 3-4-1. 1H NMR of a 1:1 mixture of amide 1b or 1c with [Pd(CH3CN)4](BF4)2 45 3-5-1. 1H NMR of 1a-metal complexes with variable stoichiometry 46