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本文合成了[Co(tp)_2(Me-en)]ClO_4(tp:2-羟基-2,4,6-环庚三烯-1-酮负离子;Me-en:N-甲基乙二胺)三元不对称配合物,用离子交换法分离了该配合物的Λ(R)Δ(S)和Λ(S)Δ(R)两对对映体,用高效液相色谱法测定了对映体的不对称配位氮的翻转速率常数K_(ep)(差向立体异构化速率常数),用~1HNMR法测定了对映体的不对称配位氮的重氢化(质子交换)速率常数k_D,并与同属CoO_4N_2型的Na[Co(OX)_2(Me-en)](OX:草酸根)、[Co(acac)_2(Me-en)]ClO_4(acac:2,4-戊二酮负离子)配合物的k_(ep)、k_D值进行了比较,讨论了影响质子交换、不对称氮翻转速率的因素及反应机理。
In this paper, [Co (tp) _2 (Me-en)] ClO_4 (tp: 2-hydroxy-2,4,6-cycloheptatrien- ) Ternary asymmetric complexes, the two enantiomers of Λ (R) Δ (S) and Λ (S) Δ (R) of the complex were separated by ion exchange method and their enantiomeric excess was determined by high performance liquid chromatography The asymmetric coordination enantiomer nitrogen turnover rate constant K ep ep (epimeric stereoisomerization rate constant), the ~ 1HNMR determination of enantiomer asymmetric coordination nitrogen dehydro (proton exchange) rate Constant k_D, and are related to Na [Co (OX) _2 (Me-en)] (OX: oxalate), [Co (acac) _2 (Me-en)] ClO_4 (acac: Dione anion) k k (ep), k_D value were compared, discussed the proton exchange, asymmetric nitrogen turnover rate of the factors and reaction mechanism.