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The role of the sulfur 3d orbitals in bond formation in sulfur‐containing compounds
Author(s) -
Xiao Li,
Li LeMin,
Liang ZhenXuan
Publication year - 1989
Publication title -
acta chimica sinica english edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 0256-7660
DOI - 10.1002/cjoc.19890070403
Subject(s) - chemistry , sulfur , valence bond theory , molecular orbital theory , atomic orbital , molecular orbital , molecular orbital diagram , natural bond orbital , orbital hybridisation , valence (chemistry) , linear combination of atomic orbitals , molecule , computational chemistry , chemical bond , chemical physics , crystallography , density functional theory , organic chemistry , physics , quantum mechanics , electron
Abstract The role of the sulfur 3d orbitals in bond formation is discussed by taking into account the influence of the environment on the orbitals of the sulfur atom in the molecules. The calculation results of a series of prototype molecules containing sulfur such as SF 2 SF 4 , NSF 3 , SF 0 , H 2 S are reported. It is convincingly shown that in highly electronegative environment the energy levels of the sulfur 3d orbitals are reduced to the vicinity of those of the ligand valence orbitals and their spatial distributions are contracted to the bonding area, and therefore they can participate in bond formation to a certain extent, which is enhanced by the formation of the d‐p π back bonds. It seems that the result reported in this paper is helpful for the solution of the long‐standing debate about the sulfur 3d orbital participation in bond formation.