PROTOTYPAL 1,2,3,5-DITHIADIAZOLYL AND 1,2,3,5-DISELENADIAZOLYL [HCN2E2].(E = S, SE) - MOLECULAR AND ELECTRONIC-STRUCTURES OF THE RADICALS AND THEIR DIMERS, BY THEORY AND EXPERIMENT

The reactions of N,N,N'-tris(trimethylsilyl)formamidine with ECl2 (E = S, Se) afford 1,2,3,5-dithia- and 1,2,3,5-diselenadiazolium chloride, which can be reduced with triphenylantimony to the corresponding dith ia- and diselenadiazolyl radicals [HCN2E2].. The solid state structure of the cofacial dimer [HCN2S2]2 has been determined by X-ray diffract ion; crystals of [HCN2S2]2 belong to the monoclinic space group P2(1)/ n, with a = 6.833(6), b = 16.463(4), c = 19.161(4) angstrom, beta = 93 .57(4)degrees, FW = 210.30, Z = 12. The crystal structure consists of stacked dimers, with three dimers in the asymmetric unit. Along the st acking axis the mean intradimer S- - -S contact is 3.11 angstrom; the mean interdimer contact is 3.76 angstrom. Ab initio calculations with split-valence and larger basis sets have been employed to evaluate the structures and energies of both the gas phase radicals and their dime rs. Minor changes in geometry are predicted upon association of the mo nomers; this relative structural invariance is consistent with low bin ding energies, the best predictions (including zero point vibrational energy corrections) being ca. 4 kcal/mol (for E = S) and ca. 10 kcal/m ol (for E = Se). Theory also provides spin distributions to support th e interpretation of the observed ESR parameters (for E = S), confirms the a2 symmetry of the SOMO, yields Koopmans' theorem and DELTASCF ion ization potentials for analysis of the PE spectra of the radicals, and furnishes vibrational frequencies and infrared intensities of the sul fur radical. The latter facilitate assignment of the gas-phase IR spec trum.