Department of Applied Chemistry, School of Engineering, Chubu University, Kasugai, 487-8501, Japan.
Dalton Trans. 2011 Aug 28;40(32):8156-69. doi: 10.1039/c1dt10208g. Epub 2011 Jul 13.
A series of selenium and tellurium bis(carbodithioates and carbothioates) were synthesized. X-Ray structure analysis revealed that Se(SSCC(6)H(4)OMe-2)(2), Te(SSCC(6)H(4)OMe-2)(2) and Te(SSCC(6)H(4)Me-4)(2) have trapezoidal-planar configuration of ES(4) (E = Se, Te) and despite the larger atomic radii, the C=S···Te distances in Te(SSCC(6)H(4)OMe-2)(2) are comparable to those in the corresponding selenium derivatives Se(SSCC(6)H(4)OMe-2)(2). Molecular-orbital calculations performed on compounds E(E'SCR)(2) (E = S, Se, Te; E' = O, S; R = Me, Ph, C(6)H(4)OMe-2) showed that the syn-conformers of Se(SSCR)(2) and Te(SSCR)(2) are more stable than the corresponding anti-ones, while, in the case of carbothioic acid derivatives, E(SOCR)(2) showed that their anti-conformers are all more stable than the corresponding syn-ones. Natural bond orbital (NBO) analyses of these dithio-compounds revealed that two types of orbital interactions, n(S(1))→σ*(E-S(2)) and n(O)→σ*(E-S(2)), play a role in the bonding of ES(2)S(1)CC(6)H(4)OMe-2 (E = Se, Te) and the former play a particularly predominant role.
一系列硒和碲双（碳二硫代酸酯和碳硫代酸酯）被合成。X 射线结构分析表明，Se(SSCC(6)H(4)OMe-2)(2)、Te(SSCC(6)H(4)OMe-2)(2)和 Te(SSCC(6)H(4)Me-4)(2)具有 ES(4)（E=Se、Te）的梯形平面构型，尽管原子半径较大，但 Te(SSCC(6)H(4)OMe-2)(2)中的 C=S···Te 距离与相应的硒衍生物 Se(SSCC(6)H(4)OMe-2)(2)中的相当。对化合物 E(E'SCR)(2)（E=S、Se、Te；E'=O、S；R=Me、Ph、C(6)H(4)OMe-2）进行分子轨道计算表明，Se(SSCR)(2)和 Te(SSCR)(2)的顺式构象比相应的反式构象更稳定，而在碳硫代酸酯衍生物的情况下，E(SOCR)(2)表明其反式构象都比相应的顺式构象更稳定。这些二硫化合物的自然键轨道（NBO）分析表明，两种类型的轨道相互作用，n(S(1))→σ*(E-S(2))和 n(O)→σ*(E-S(2))，在 ES(2)S(1)CC(6)H(4)OMe-2（E=Se、Te）的成键中起作用，前者起着特别主要的作用。
