REACTIONS OF LASER-ABLATED MG, CA, SR, AND BA ATOMS WITH HYDROGEN-CYANIDE IN EXCESS ARGON - MATRIX INFRARED-SPECTRA AND DENSITY-FUNCTIONAL CALCULATIONS ON NOVEL ISOCYANIDE PRODUCTS
Dv. Lanzisera et L. Andrews, REACTIONS OF LASER-ABLATED MG, CA, SR, AND BA ATOMS WITH HYDROGEN-CYANIDE IN EXCESS ARGON - MATRIX INFRARED-SPECTRA AND DENSITY-FUNCTIONAL CALCULATIONS ON NOVEL ISOCYANIDE PRODUCTS, The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 101(50), 1997, pp. 9666-9672
Laser-ablated alkaline earth metal atoms reacting with hydrogen cyanid
e in the presence of excess argon produce matrix-isolated linear metal
isocyanides, MNC, but no noticeable amount of the corresponding cyani
de isomer, MCN. Supplemental experiments with DCN show that, unlike th
e corresponding beryllium reactions, no products containing hydrogen a
re formed. Experiments with isotopically enriched (HCN)-C-13 yield (MN
C)-C-13 shifted 40 cm(-1) from (MNC)-C-12 in the C=N stretching freque
ncy, with the isotopic shift virtually independent of the alkaline ear
th metal. As the mass of the group 2 metal increases, the C=N frequenc
y decreases and the absorption becomes broader, the latter feature ind
icating a decreasingly rigid linear geometry. The lack of MCN indicate
s that the products form via attack of the energetic metal on the nitr
ogen atom, instead of through insertion into the C-H bond.