Two isomeric phosphacarboranes 2,1- and 6,1-PCB(8)H(9), the first representatives of the 10-vertex closo phosphacarborane Series.
Two isomeric phosphacarboranes 2,1- and 6,1-PCB(8)H(9), the first representatives of the 10-vertex closo phosphacarborane Series.
复制标题
两种异构磷碳硼烷 2,1- 和 6,1-PCB(8)H(9)，是 10 顶点闭合磷碳硼烷系列的第一个代表。
作者：
J. Holub;M. Bakardjiev;B. Štíbr;D. Hnyk;O. Tok;B. Wrackmeyer
在PS存在下，花生四烯酸-4-CB（8）H（14）与PCl（3）的反应（PS =质子海绵= 1，8-二甲氨基萘）（二氯甲烷，室温，24小时）产生中性磷碳硼烷闭合-2，1-PCB（8）H（9）（35%产率），而nido-1-CB（8）H（12）的类似反应得到异构体化合物closo-6，1-PCB（8）H（9）（27%产率）。采用从头算/GIAO/NMR（（1）H，（11）B，（13）C）方法对两个化合物的结构进行了推导。在6- 31 G * 基组的相关理论水平（MP2）上优化的结构被用作计算GIAO-SCF/II和GIAO-MP2/II的（11）B和（13）C化学位移的基础，后者显示出与实验数据的极好的一致性。
The reaction between arachno-4-CB(8)H(14) and PCl(3) in the presence of PS (PS = proton sponge = 1,8-dimethylamino naphthalene) (dichloromethane, rt, 24 h) produced the neutral phosphacarborane closo-2,1-PCB(8)H(9) (35% yield), while a similar reaction of nido-1-CB(8)H(12) gave the isomeric compound closo-6,1-PCB(8)H(9) (27% yield). The structures of both compounds were derived on the basis of the combined ab initio/GIAO/NMR ((1)H, (11)B, (13)C) approach. The optimized structures at a correlated level of theory (MP2) with 6-31G* basis set were used as a basis for calculations of the (11)B and (13)C chemical shifts at GIAO-SCF/II and GIAO-MP2/II, the latter showing excellent agreement with experimental data.