Experimental and theoretical study of the coordination of 1,2,4-triazolato, tetrazolato, and pentazolato ligands to the [K(18-crown-6)]+ fragment.

Treatment of 3,5-diisopropyltriazole, 3,5-diphenyltriazole, 3,5-di-3-pyridyltriazole, phenyltetrazole, pyrrolidinyltetrazole, or tert-butyltetrazole with equimolar quantities of potassium hydride and 18-crown-6 in tetrahydrofuran at ambient temperature led to slow hydrogen evolution and formation of (3,5-diisopropyl-1,2,4-triazolato)(18-crown-6)potassium (88%), (3,5-diphenyl-1,2,4-triazolato)(tetrahydrofuran)(18-crown-6)potassium (87%), (3,5-di-3-pyridyl-1,2,4-triazolato)(18-crown-6)potassium (81%), (phenyltetrazolato)(18-crown-6)potassium (94%), (pyrrolidinyltetrazolato)(18-crown-6)potassium (90%), and (tert-butyltetrazolato)(18-crown-6)potassium (94%) as colorless crystalline solids. (1,2,4-Triazolato)(18-crown-6)potassium was isolated as a hemi-hydrate in 81% yield upon treatment of 1,2,4-triazole with potassium metal in tetrahydrofuran. The X-ray crystal structures of these new complexes were determined, and the solid-state structures consist of the nitrogen heterocycles bonded to the (18-crown-6)potassium cationic fragments with eta2-bonding interactions. In addition, (3,5-diphenyl-1,2,4-triazolato)(tetrahydrofuran)(18-crown-6)potassium has one coordinated tetrahydrofuran ligand on the same face as the 3,5-diphenyl-1,2,4-triazolato ligand, while (3,5-di-3-pyridyl-1,2,4-triazolato)(18-crown-6)potassium forms a polymeric solid through coordination of the distal 3-pyridyl nitrogen atoms to the potassium ion on the face opposite the 1,2,4-triazolato ligand. The solid-state structures of the new complexes show variable asymmetry in the potassium-nitrogen distances within the eta2-interactions and also show variable bending of the heterocyclic C2N3 and CN4 cores toward the best plane of the 18-crown-6 ligand oxygen atoms. Molecular orbital and natural bond order calculations were carried out at the B3LYP/6-311G(d,p) level of theory on the model complex, (phenyltetrazolato)(18-crown-6)potassium, and demonstrate that the asymmetric potassium-nitrogen distances and bending of the CN4 core toward the 18-crown-6 ligand are due to hydrogen bond-like interactions between filled nitrogen-based orbitals and carbon-hydrogen sigma orbitals on the 18-crown-6 ligands. Calculations carried out on the model pentazolato complex (pentazolato)(18-crown-6)potassium predict a structure in which the pentazolato ligand N5 core is bent by 45 degrees toward the best plane of the 18-crown-6 oxygen atoms. Such bending is induced by the formation of intramolecular nitrogen-hydrogen-carbon hydrogen bonds. Examination of the solid-state structures of the new complexes reveals many intramolecular and intermolecular nitrogen-hydrogen distances of < or =3.0 A which support the presence of nitrogen-hydrogen-carbon hydrogen bonds.