A new class of flexible polydentate bis(amidine) ligands L1–5H2 exhibits versatile coordination behavior towards Group 11 metal halides. L1H2 reacts with CuCl to yield the dichloro-dicopper complex [L1H2(CuCl)2] (1). X-ray crystallography reveals that CuCl (2 equiv.) inserts into the two intramolecular NH…N' hydrogen bonds of L1H2 to form NH…Cl–Cu–N' hydrogen bridges. Both cuprous ions adopt linear coordination geometry. Similarly, an isostructural digold complex [L1H2(AuCl)2] (2) was obtained from L1H2 and 2 equiv. of [(Me2S)AuCl]. However, L1H2 and AgCl (2 equiv.), using pyridine as solvent, produced the unusual coordination polymer [(L1H2)2(py)2(AgCl)3]n (3) in the crystalline state. Complex 3 shows two distinct NH…Cl–Ag–N' hydrogen bridge motifs and either trigonal-planar or tetrahedral coordination environments of the silver ions. This presentation also includes the synthesis and solid-state structures of the ligands L1–5H2. The unusual dynamic behavior of complexes 1–3 in solution is also discussed.

Group 11 metal chloride bis(amidine) complexes upon insertion into NH…N' hydrogen bonds: Synthesis, structures, and molecular dynamics in solution

2019 Spring National Meeting

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