作　　者： ; ; ; ; ; ; ;

机构地区： 中国科学院福建物质结构研究所结构化学国家重点实验室

出　　处： 《高等学校化学学报》 1998年第10期1650-1653,共4页

摘　　要： 化合物（Ｅｔ４Ｎ）２［Ｐｄ２（ｍｐ）２（Ｈｍｐ）２］（１）（Ｈ２ｍｐ＝２－巯基苯酚）的１ＨＮＭＲ谱中芳氢Ｈ１６的峰出现在δ８．７９处，与预测值（δ７．１）相差１．７，这是由于Ｈ１６与配位硫Ｓ２原子之间存在弱相互作用，即新型的ｓｐ２Ｃ—Ｈ…Ｓ之间的氢键作用．原子间距离Ｃ１６…Ｓ２（０．３６１ｐｍ）和Ｈ１６…Ｓ２（０．２９５ｐｍ）分别小于相应原子的范德华半径之和（０．３７０ｐｍ和０．３０５ｐｍ），Ｃ１６—Ｈ１６…Ｓ２角为１２８．１°，证明了这种新型氢键的存在．此外，在分子振动光谱中观察到这种氢键的作用使得芳氢νＣ—Ｈ出现在低于３０００ｃｍ－１处．通过与类似物［Ｐｄ２（ＰＰｈ３）２（Ｈｍｐ）２Ｃｌ２］（２）的比较，以及１在ＤＭＳＯ溶剂中仍然保持Ｏ—Ｈ…Ｏ和Ｃ—Ｈ…Ｓ这２种氢键的事实，表明Ｃ—Ｈ…Ｓ之间的作用，对１的配体Ｈｍｐ中的苯环与Ｐｄ２Ｓ２平面之间的夹角偏离９０°可能是有贡献的． Weak interaction between the H16 atom of aromatic hydrocarbon and the coordinated S2 atom, a new type of hydrogen bond sp 2 C H…S, has been suggested in explaining the phenomenon of the 1H NMR H16 peak of the compound(Et 4N) 2 Pd 2(mp) 2(Hmp) 2 (H 2mp=2 mercaptophenol) appearing at δ 8.79 which is 1.7 lower than the expected value δ 7.1 . The distances of C16…S2(0.361 pm) and H16…S2(0.295 pm) lowing the sum of the van der Waals radii(0.325 pm) for the corresponding atoms, respectively, demonstrates the existence of the hydrogen bond. In addition, it has been observed that the C H of aromatic hydrocarbon shifts to 2 998 cm -1 resulting from the sp 2 C H…S hydrogen interaction. Comparison with the structure of the analogues compound Pd 2(PPh 3) 2(Hmp) 2Cl 2 and the remaining of the O H…O and C H…S hydrogen bonds even in DMSO suggest that the torsion angle between the phenyl linking to the bridging sulfur atom and Pd 2S 2 plane deviated from 90° may be contributed partially from the C H…S hydrogen bonding.

关 键 词： 分子内 氢键 巯基苯酚 芳氢 配位硫原子

领　　域： [理学] [理学]