Squeezing the [Cu-OH...H2O-Cu]3+ bridge by cryptate encapsulation.
Squeezing the [Cu-OH...H2O-Cu]3+ bridge by cryptate encapsulation.
复制标题
通过穴状化合物封装挤压 [Cu-OH...H2O-Cu]3 桥。
作者：
A. Bond;S. Derossi;F. Jensen;F. B. Larsen;C. McKenzie;J. Nelson
用 Cu(II) 处理穴状配体 L(1) 生成 H3O2(-) 桥接二铜 (II) 穴状化合物 2，其中客体阴离子通过 O-O 距离显着缩短至 2.325(9) A 来响应空间约束； B3LYP/6-31(d) 水平的计算优化表明桥接 O-H...O H 键是弯曲的（大约 157 度），但桥接 H 原子交换的势垒较低（<4 kJ mol(-1)）。这种穴状化合物，而不是最近声称源自溶剂 C-C 键断裂的 [Cu2L(1)muCN]3+ 物质，是最初形成的反应产物 1 的乙腈重结晶的产物。
Treatment of cryptand L(1) with Cu(II) generates a H3O2(-)-bridged dicopper(II) cryptate, 2, where the guest anion has responded to steric constraint by a significant shortening of the O-O distance to 2.325(9) A; computational optimization at the B3LYP/6-31(d) level suggests that the bridging O-H...O H-bond is bent (approximately 157 degrees) but that the barrier to interchange of the bridging H atom is low (<4 kJ mol(-1)). This cryptate, rather than the [Cu2L(1)muCN]3+ species recently claimed to derive from cleavage of the C-C bond of the solvent, is the product of acetonitrile recrystallization of the initially formed reaction product, 1.