Kato Masahiro, Kojima Kazunori, Okamura Taka-aki, Yamamoto Hitoshi, Yamamura Takeshi, Ueyama Norikazu
Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan.
Inorg Chem. 2005 May 30;44(11):4037-44. doi: 10.1021/ic0481780.
A novel series of bis(carbamoylthiophenolato)mercury(II) complexes, [Hg(S-RNHCOC6H4)2] (1, R = 2-t-Bu; 2, R = 2-CH3; 3, R = 2-C6H5CH2; 4, R = 4-t-Bu), and a tetrakis(carbamoylthiophenolato)mercury(II) complex, (NEt4)2[Hg-(S-2-CH3NHCOC6H4)4] (5), were synthesized and characterized by 1H NMR, IR, 199Hg NMR, and crystallographic analyses. The bis(carbamoylthiophenolato)mercury complexes 1-3 do not have intramolecular NH...S hydrogen bonds between the amide NH group and the sulfur atom coordinated to mercury, whereas the tetrakis(thiophenolato)mercury complex 5 does have an intramolecular NH...S hydrogen bond. A relatively weak NH...S hydrogen bond in 5 can be seen in the 1H NMR spectra and the IR spectra in chloroform and in the solid state. The 199Hg NMR spectra in bis(carbamoylthiophenolato)mercury complexes 1-4 show a downfield shift, with an increase in the flow of electrons to mercury(II) from the oxygen atom due to the intramolecular Hg...O bonding interaction. Conversely, the 199Hg NMR spectra in 5 show a high-field shift with a decrease in the flow of electrons to mercury(II) from the sulfur atom due to the intramolecular NH...S hydrogen bond.
合成了一系列新型的双（氨基甲酰硫酚根）汞（II）配合物[Hg(S-RNHCOC6H4)2]（1，R = 2-叔丁基；2，R = 2-甲基；3，R = 2-苯甲基；4，R = 4-叔丁基）和一种四（氨基甲酰硫酚根）汞（II）配合物(NEt4)2[Hg-(S-2-CH3NHCOC6H4)4]（5），并通过1H NMR、IR、199Hg NMR和晶体学分析对其进行了表征。双（氨基甲酰硫酚根）汞配合物1-3在酰胺NH基团与配位至汞的硫原子之间不存在分子内NH...S氢键，而四（硫酚根）汞配合物5存在分子内NH...S氢键。在5中相对较弱的NH...S氢键可在1H NMR光谱以及氯仿和固态的IR光谱中观察到。双（氨基甲酰硫酚根）汞配合物1-4的199Hg NMR光谱显示出向低场移动，这是由于分子内Hg...O键相互作用导致从氧原子流向汞（II）的电子流增加。相反，5的199Hg NMR光谱显示出向高场移动，这是由于分子内NH...S氢键导致从硫原子流向汞（II）的电子流减少。
