[Co(tp)_2(Me_3en)]ClO_4配合物不对称配位氮原子的重氢化研究

Studies on the Deuteration at the Chiral Nitrogen of Bis(tropolonato) (N, N, N' -Trimethyl ethyl enediamine) Cobalt (Ⅲ) Complexes

合成了[Co(tp)_2(Me_3en)]ClO_4配合物,用离子交换法提纯和分离了该配合物的2对对映体:Δ(R)∧(S)、Δ(S)∧(R)异构体,用高分辨NMR法分别测定了这2对对映体的不对称配位氮原子的重氢化速率常数k_D值分别为:1.0×10~5和1.8×10~4L·mol^(-1)·s^(-1)(34.0℃),讨论了影响重氢化作用的因素。

Bis(tropolonato)(N,N,N'-trimethylethylenediamine) Cobalt(Ⅲ) complex, [Co(tp)2 (Me3en)]ClO4(Me3en = N,N,N' -trimethylethylenediamine, tp=univalent anion of tropolone), was synthesized. The complex was purified and separated into two racemic pairs (△(R) (S) and △(S) (R)-isomers) by the ion exchange method. The rate constants of deuteration(kD) at the chiral nitrogen were measured by high-resolution 1H NMR spectrometry. The value of kD at 34. 0℃ was 1.0×105 L.mol-1.s-1 for △(R) (S)-isomer and 1. 8 × 104 L.mol-1.s-1 for △(S) (R)-isomer. The factors which influence the deuteration are also discussed in this paper.