物理化学学报
物理化學學報
물이화학학보
ACTA PHYSICO-CHIMICA SINICA
2013年
6期
1183-1191
,共9页
赵檑%万仕刚%陈成栋%林以玑%方雪明%章慧*
趙檑%萬仕剛%陳成棟%林以璣%方雪明%章慧*
조뢰%만사강%진성동%림이기%방설명%장혜*
半醌Fe(III)络合物%镜面对称性破缺%绝对构型%固体CD光谱%单晶X射线衍射
半醌Fe(III)絡閤物%鏡麵對稱性破缺%絕對構型%固體CD光譜%單晶X射線衍射
반곤Fe(III)락합물%경면대칭성파결%절대구형%고체CD광보%단정X사선연사
Semiquinone Fe(III) complexes%Mirror symmetry breaking%Absolute configuration%Solid-state CD spectroscopy%Single crystal X-ray diffraction
以2-苯胺基-4,6-二叔丁基苯酚(H2L)和 FeCl2·4H2O 为原料制备了一对手性半醌 Fe(III)络合物Λ-mer-[Fe(LISQ)3]和Δ-mer-[Fe(LISQ)3](LISQ:2-苯亚胺基-4,6-二叔丁基苯酚, mer :经式构型),通过单晶X射线衍射分析结合单晶压制片膜的固体圆二色(CD)光谱确定了该络合物的绝对构型,在此基础上建立了此类半醌络合物[M(LISQ)3](M=Cr, Fe, Co)的惟手性金属中心绝对构型与固体CD光谱之间的关联.此外,还对10份合成的[Fe(LISQ)3]的大宗产物粉末与单晶的固体CD谱进行了比对分析,以及对1份合成产物进行10次重结晶的固体CD 光谱表征.研究表明该化合物在结晶过程中发生了镜面对称性破缺(MSB),对映体过量(ee)值在15%-100%之间.
以2-苯胺基-4,6-二叔丁基苯酚(H2L)和 FeCl2·4H2O 為原料製備瞭一對手性半醌 Fe(III)絡閤物Λ-mer-[Fe(LISQ)3]和Δ-mer-[Fe(LISQ)3](LISQ:2-苯亞胺基-4,6-二叔丁基苯酚, mer :經式構型),通過單晶X射線衍射分析結閤單晶壓製片膜的固體圓二色(CD)光譜確定瞭該絡閤物的絕對構型,在此基礎上建立瞭此類半醌絡閤物[M(LISQ)3](M=Cr, Fe, Co)的惟手性金屬中心絕對構型與固體CD光譜之間的關聯.此外,還對10份閤成的[Fe(LISQ)3]的大宗產物粉末與單晶的固體CD譜進行瞭比對分析,以及對1份閤成產物進行10次重結晶的固體CD 光譜錶徵.研究錶明該化閤物在結晶過程中髮生瞭鏡麵對稱性破缺(MSB),對映體過量(ee)值在15%-100%之間.
이2-분알기-4,6-이숙정기분분(H2L)화 FeCl2·4H2O 위원료제비료일대수성반곤 Fe(III)락합물Λ-mer-[Fe(LISQ)3]화Δ-mer-[Fe(LISQ)3](LISQ:2-분아알기-4,6-이숙정기분분, mer :경식구형),통과단정X사선연사분석결합단정압제편막적고체원이색(CD)광보학정료해락합물적절대구형,재차기출상건립료차류반곤락합물[M(LISQ)3](M=Cr, Fe, Co)적유수성금속중심절대구형여고체CD광보지간적관련.차외,환대10빈합성적[Fe(LISQ)3]적대종산물분말여단정적고체CD보진행료비대분석,이급대1빈합성산물진행10차중결정적고체CD 광보표정.연구표명해화합물재결정과정중발생료경면대칭성파결(MSB),대영체과량(ee)치재15%-100%지간.
@@@@A pair of chiral o-iminobenzosemiquinonato Fe(III) complexes, Λ-mer-[Fe(LISQ)3] and Δ-mer-[Fe(LISQ)3] (LISQ: 2-phenylimino-4,6-di-tert-butylphenol, mer : meridian configuration), were synthesized from 2-anilino-4,6-di-tert-butylphenol (H2L) and FeCl2·4H2O. Their absolute configurations were determined by single crystal X-ray diffraction (XRD) and solid-state circular dichroism (CD) spectra (the same single crystal for XRD was dispersed in KCl). Correlations between the absolute configurations of the chiral-at-metal o-iminobenzosemiquinonato M(III) complexes [M(LISQ)3] (M=Cr, Fe, Co) and their solid-state CD spectra were also established. Comparison between solid-state CD spectra of the bulk samples from 10 different syntheses and their single crystals were thoroughly analyzed. The solid-state CD spectra of the powdered samples from 10 different crystal izations of one product were characterized. These studies indicated that mirror symmetry breaking (MSB) occurred during the crystal ization process of the Fe(III) complexes and their enantiomeric excess (ee) values were between 15% and 100%.
