Hydrogen bonds and dispersion forces serving as molecular locks for tailored Group 11 bis(amidine) complexes

Janet Arras, Kennesaw State University
Omar Ugarte Trejo, Kennesaw State University
Nattamai Bhuvanesh, Texas A&M University
Michael Stollenz, Kennesaw State University


A flexible polydentate bis(amidine) ligand LH2, LH2 = {CH2NH(tBu)C 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 N-2-(6-MePy)}2, operates as a molecular lock for various coinage metal fragments and forms the dinuclear complexes [LH2(MCl)2], M = Cu (1), Au (2), the coordination polymer [{(LH2)2(py)2(AgCl)3}(py)3]n (3), and the dimesityl-digold complex [LH2(AuMes)2] (4) by formal insertion of MR fragments (M = Cu, Ag, Au; R = Cl, Mes) into the N-H⋯N hydrogen bonds of LH2 in yields of 43-95%. Complexes 1, 2, and 4 adopt C2-symmetrical structures in the solid state featuring two interconnected 11-membered rings that are locked by two intramolecular N-H⋯R-M hydrogen bonds. QTAIM analyses of the computational geometry-optimized structures 1a, 2a, and 4a reveal 13, 11, and 22 additional bond critical points, respectively, all of which are related to weak intramolecular attractive interactions, predominantly representing dispersion forces, contributing to the conformational stabilization of the C2-symmetrical stereoisomers in the solid state. Variable-temperature 1H NMR spectroscopy in combination with DFT calculations indicate a dynamic conformational interconversion between two C2-symmetrical ground state structures in solution (ΔG‡c = 11.1-13.8 kcal mol−1), which is accompanied by the formation of an intermediate possessing Ci symmetry that retains the hydrogen bonds.