Shubina E S, Tikhonova I A, Bakhmutova E V, Dolgushin F M, Antipin M Y, Bakhmutov V I, Sivaev I B, Teplitskaya L N, Chizhevsky I T, Pisareva I V, Bregadze V I, Epstein L M, Shur V B
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow.
Chemistry. 2001 Sep 3;7(17):3783-90. doi: 10.1002/1521-3765(20010903)7:17<3783::aid-chem3783>3.0.co;2-1.
It has been shown by IR and NMR spectroscopy that cyclic trimeric perfluoro-o-phenylenemercury (o-C6F4-Hg)3 (1) is capable of binding closo-[B10H10]2- and closo-[B12H12]2- anions to form complexes [(o-C6F4Hg)3]2- (2), [[(o-C6F4Hg)3]2(B10H10)]2-(3), [(o-C6F4Hg)3]2- (4), and [[(o-C6F4Hg)3]2(B12H12)]2- (5). According to IR data, the bonding of the [B10H10]2- and [B12H12]2- ions to the macrocycle in these complexes is accomplished through the formation of B-H-Hg bridges. Complexes 2, 3, and 5 have been isolated in analytically pure form and have been characterized by spectroscopic means. X-ray diffraction studies of 3 and 5 have revealed that these compounds have unusual sandwich structures, in which the polyhedral di-anion is located between the planes of two molecules of 1 and is bonded to each of them through two types of B-H-Hg bridges. One type is the simultaneous coordination of a B-H group to all three Hg atoms of the macrocycle. The other type is the coordination of a B-H group to a single Hg atom of the cycle. According to X-ray diffraction data, complex 2 has an analogous but half-sandwich structure. The obtained complexes 2-5 are quite stable; their stability constants in THF/acetone (1:1) at 20 degrees C have been determined as 1.0 x 10(2)Lmol(-1), 2.6 x 10(3)L(2)mol(2), 0.7 x 10(2)Lmol(-1), and 0.98 x 10(3)L(2)mol(-2), respectively.
红外光谱和核磁共振光谱表明，环状三聚全氟邻苯撑汞（o-C6F4-Hg）3（1）能够与闭式-[B10H10]2-和闭式-[B12H12]2-阴离子结合形成配合物[(o-C6F4Hg)3]2-（2）、[[(o-C6F4Hg)3]2(B10H10)]2-（3）、[(o-C6F4Hg)3]2-（4）和[[(o-C6F4Hg)3]2(B12H12)]2-（5）。根据红外数据，这些配合物中[B10H10]2-和[B12H12]2-离子与大环的键合是通过形成B-H-Hg桥来实现的。配合物2、3和5已被分离成分析纯形式，并通过光谱手段进行了表征。对3和5的X射线衍射研究表明，这些化合物具有不寻常的夹心结构，其中多面体二阴离子位于两个1分子平面之间，并通过两种类型的B-H-Hg桥与每个分子相连。一种类型是B-H基团同时与大环的所有三个Hg原子配位。另一种类型是B-H基团与环上的单个Hg原子配位。根据X射线衍射数据，配合物2具有类似但为半夹心的结构。所得到的配合物2-5相当稳定；它们在20℃下于四氢呋喃/丙酮（1:1）中的稳定常数分别测定为1.0×10(2)Lmol(-1)、2.6×10(3)L(2)mol(2)、0.7×10(2)Lmol(-1)和0.98×10(3)L(2)mol(-2)。
