《through hydrogen bonding》.pdfVIP

International Journal of Mass Spectrometry 201 2000 87–100 A study of complexes Mg NH and Ag NH , where n 3 n 3 n 1–8: Competition between direct coordination and solvation through hydrogen bonding Tamer Shoeib*, Rebecca K. Milburn, Gregory K. Koyanagi, Vitali V. Lavrov, Diethard K. Bohme, K.W. Michael Siu, Alan C. Hopkinson Department of Chemistry, York University, Toronto, Ontario, M3J 1P3, Canada Received 5 October 1999; accepted 12 November 1999 Abstract Density functional calculations at B3LYP/6-31 G d and B3LYP/DZVP are reported for Mg NH , where n 1–6 and 3 n for some solvated ions Mg NH . . . NH n 1–3, 6 . After correction for basis set superposition errors, the enthalpies 3 n 3 for sequential addition of NH3 to Mg resulting from direct coordination to the metal are 38.1, 26.6, 21.2, 13.7, 12.1, and 11.3 kcal mol 1. The free energies for these same addition reactions are all negative, although for complexes with n 4 the values are very small. Attempts at optimising structures with higher coordination numbers all resulted in the formation of solvated octahedral complexes. Enthalpies for solvation through hydrogen bonding to one of the ligated NH3 molecules are all less than 16 kcal mol1 and decrease rapidly as the number of ligated NH3 molecules increases. Molecular orbital calculations at B3LYP/DZVP have been used to optimise structures for ions Ag NH , where n 1–6. The ?ve-coordinate and 3 n six-coordinate structures have very small binding enthalpies 4.3 and 2.6 kcal mol1 and the free energies for formation of these ions are positive. The binding energies for the addition of the ?rst and second NH3 molecules added to Ag are 40.1 and 36.1 kcal mol1, while those for the third and fourth additions are much smaller 15.1 and 11.0 kcal mol1 . Adducts up to n 3 have been detected in electrospray experiments. The ?rst three adducts of Ag with NH have been formed in the 3 selected io