含超价硫三元无机杂环化合物的理论研究(Ⅰ)

本文应用ab initio方法,研究了含超价硫化合物分子中硫原子的3d轨道的成键作用,并使用Martagh-Sargent梯度优化法,预测了该化合物的几何构型。指出硫二氮三元无机杂环中,d-pπ键在S-N间起重要作用。

THEORETICAL STUDY OF HYPERVALENT SULFUR CONTAINING THREE-MEMBERED INORGANIC HETEROCYCLIC COMPOUNDS

The hypervalcnt surfur containing compound has been studied with ab invtio method comparison, we optimized the cxponcnt(d) of sulfur in SO2 and got the value different from that in SF4(1.25). The geometry of SO2 has been optimized on the conton of 3s2p]d/ 2s1p] (bases set I ) and 4s3p1d/ 3s2p/ 2s](bases set II ) resptetivclv, arc better than the results obtained by using the bases of STO-3G, 3-21G or 3-2IC pared with the expcriment; that indicated the d orbital involving is imentantion the multiplication of calculated energy levels with Rouin plained the PES of SO2. We adopt O2SN2H2 as the model molecule for studying the kin molecule O2SN2RR From the population analysis and this digram O2SN2H2 with SO- and HN-NH, we have found that the valcnco Smiolculc O2SN 648. which increased some about 2 from that in SO2. The d- p a-bonding play an role in stabilizing the molecuic.