Synthesis and vibrational circular dichroism of enantiopure chiral oxorhenium(V) complexes containing the hydrotris(1-pyrazolyl)borate ligand
Synthesis and vibrational circular dichroism of enantiopure chiral oxorhenium(V) complexes containing the hydrotris(1-pyrazolyl)borate ligand
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DOI：
10.1021/ic061418m
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发表时间：
2006-12-11
影响因子：
4.6
通讯作者：
Nafie, Laurence A.
中科院分区：
文献类型：
--
作者：
Lassen, Peter R.;Guy, Laure;Nafie, Laurence A.
本文研究了六种含三（1-吡唑基）硼酸氢（Tp）配体的手性氧合铼（V）配合物的红外光谱和振动圆二色谱（VCD）。这些配合物是观察宇称破坏（由于弱核力的对称性破缺）的有希望的候选者。合成了新的手性氧合铼配合物，即[TpReO（eta（2）-O（CH 3）CH 2 CH 2 O-O，O）]（4a和4 b）非对映体和[TpReO（eta（2）-N（CH 3）CH 2 CH 2 O-N，O）]（5）和[TpReO（eta（2）-N（tBu）CH 2 CH 2 O-N，O）]（6）对映体。所有化合物都可以通过柱色谱法或手性柱上的HPLC以对映体纯的形式获得。本文研究了这些化合物和[TpReO（eta（2）-N（CH_3）CH（CH_3）CH（Ph）O-N，O）]（2）和[TpReO（eta（2）-N（CH_2）（3）CHCO_2-N，O）]（3）（分别与麻黄碱和脯氨酸衍生的手性双齿配体）的VCD光谱。这使得所有化合物的绝对构型确定连同它们的构象分析，通过比较计算和实验光谱。这是第一个VCD研究的无机配合物，进一步证明了VCD光谱在确定无机配合物的手性的适用性。
The infrared and vibrational circular dichroism (VCD) spectra of six chiral oxorhenium(V) complexes, bearing a hydrotris(1-pyrazolyl) borate (Tp) ligand, have been investigated. These complexes are promising candidates for observation of parity violation ( symmetry breaking due to the weak nuclear force). New chiral oxorhenium complexes have been synthesized, namely, [TpReO(eta(2)-O(CH3)CH2CH2O-O, O)] (4a and 4b) diastereomers and [TpReO(eta(2)-N(CH3)CH2CH2O-N,O)] (5) and [TpReO(eta(2)-N(tBu)CH2CH2O-N,O)] (6) enantiomers. All compounds could be obtained in enantiomerically pure form by using either column chromatography or HPLC over chiral columns. VCD spectroscopy of these compounds and of [TpReO(eta(2)-N(CH3)CH(CH3)CH(Ph)O-N,O)] (2) and [TpReO(eta(2)-N(CH2)(3)CHCO2-N,O)] (3) ( with chiral bidentate ligands derived, respectively, from ephedrine and proline) were studied. This allowed the absolute configuration determination of all compounds together with their conformational analysis, by comparing calculated and experimental spectra. This is the first VCD study of rhenium complexes which further demonstrates the applicability of VCD spectroscopy in determining the chirality of inorganic complexes.