Ab initio study of rearrangements on the (CH)(2)(BR)(2), R=H, and NH2 potential energy surfaces

摘要

comprehensive survey of the (CH)(2)(BH)(2) potential energy surface was carried out at the [MP4/6-311+G-(d,p)]//MP2/6-31G(d) level. Many of the classical and nonclassical isomers of the carborane surface are separated by high activation barriers, which explains why derivatives of most isomers could be prepared as stable compounds at room temperature. The transition states are grouped into two types, hydrogen migration (terminal-to-bridge and bridge-to-terminal) and group migration (BH, CH, and CH2). The rearrangement of 1,3-diamino-1,3-diboretene (1-NH2) to 1,2-diamino-1,2-diboretene (2-NH2) was computed and compared to the rearrangement in the parent (1 --> 2). The effect of the amino group is to substantially increase the barrier height and stabilize the product, 2-NH2. [References: 37]