College of Chemistry, Beijing Normal University, Beijing, 100875, People's Republic of China.
J Mol Model. 2013 Jan;19(1):299-304. doi: 10.1007/s00894-012-1518-9. Epub 2012 Aug 14.
MP2(full)/aug-cc-pVDZ(-PP) computations predict that new triangular bonding complexes CBr4...X-...H-C (where X- is a halide and H-C refers to a protic solvent molecule) consist of one halogen bond and two hydrogen bonds in the gas phase. Carbon tetrabromide acts as the donor in the halogen bond, while it acts as an acceptor in the hydrogen bond. The halide (which commonly acts as an acceptor) can interact with both carbon tetrabromide and solvent molecule (CH3CN, CH2Cl2, CHCl3) to form a halogen bond and a hydrogen bond, respectively. The strength of the halogen bond obeys the order CBr4...Cl->CBr4...Br->CBr4...I-. For the hydrogen bonds formed between various halides and the same solvent molecule, the strength of the hydrogen bond obeys the order C-H...Cl->C-H...Br->C-H...I-. For the hydrogen bonds formed between the same halide and various solvent molecules, the interaction strength is proportional to the acidity of the hydrogen in the solvent molecule. The diminutive effect is present between the hydrogen bonds and the halogen bond in chlorine and bromine triangular bonding complexes. Complexes containing iodide ion show weak cooperative effects.
MP2(full)/aug-cc-pVDZ(-PP) 计算预测，新的三角键合配合物 CBr4...X-...H-C（其中 X-是卤素，H-C 指质子溶剂分子）在气相中包含一个卤素键和两个氢键。四溴化碳在卤素键中作为供体，而在氢键中作为受体。卤素（通常作为受体）可以与四溴化碳和溶剂分子（CH3CN、CH2Cl2、CHCl3）相互作用，分别形成卤素键和氢键。卤素键的强度遵循 CBr4...Cl->CBr4...Br->CBr4...I-的顺序。对于各种卤素与相同溶剂分子之间形成的氢键，氢键的强度遵循 C-H...Cl->C-H...Br->C-H...I-的顺序。对于同一卤素与各种溶剂分子之间形成的氢键，相互作用强度与溶剂分子中氢的酸度成正比。在氯和溴三角键合配合物中，氢键和卤素键之间存在微小的影响。含碘离子的配合物表现出较弱的协同效应。
