Adding the right (or left) twist to tris-chelate complexes - coordination chemistry of chiral oxazolylphenolates with M3+ ions (M = Al or lanthanide)
Adding the right (or left) twist to tris-chelate complexes - coordination chemistry of chiral oxazolylphenolates with M3+ ions (M = Al or lanthanide)
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DOI：
10.1039/c3dt52366g
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发表时间：
2014-01-01
影响因子：
4
通讯作者：
Thomas, Christopher D.
中科院分区：
文献类型：
--
作者：
Aspinall, Helen C.;Bacsa, John;Thomas, Christopher D.
本文报道了一系列均配型三螯合物ML_3（M = Al或稀土; L =手性或非手性恶唑基酚盐或-萘酚盐）。在所有情况下，络合物结晶为mer-异构体，并且在络合物结晶时观察到完全的非对映选择性：ML 3在金属处以A-螺旋性结晶，其中L =（S）-恶唑基苯酚盐。络合物的特征在于在溶液中的NMR光谱，表现出快速的配体交换在环境温度下的稀土配合物，和缓慢的交换的NMR时标的配合物的Al;在所有情况下，mer异构体被观察到排他。报道了[YL 3] 2（L =（S）-2-[（S）-2-（S）（4-异丙基-4，5-二氢恶唑-2-基）苯酚盐），mer-[YbL 3]（L =（S）-2-（三氟甲基）苯基）-N-甲基-N-（4-异丙基-4，5-二氢恶唑-2-基）苯酚盐），（4-异丙基-4，5-二氢恶唑-2-基）-6-甲基苯酚酯）和mer-[AlL 3]（L =（S）-2-甲基-1H-吡唑-4-基）-1H-吡唑-4-基）。（4-异丙基-4，5-二氢恶唑-2-基）-6-甲基苯酚盐，L =（S）-2-（4-异丙基-4，5-二氢恶唑-2-基）-6-氰基苯酚），L =（S）-1-（4-异丙基-4，5-二氢恶唑-2-基）萘-2-醇盐，L = 1-（4，4-二甲基-4，5-二氢恶唑-2-基）萘-2-醇盐）。
A series of homoleptic tris-chelate complexes ML3 (M = Al or rare earth; L = chiral or achiral oxazolyl phenolate or -naphtholate) is reported. In all cases, complexes crystallize as mer-isomers and complete diastereoselectivity is observed on crystallization of the complexes: ML3 crystallize with A-helicity at the metal where L = (S)-oxazolylphenolate. Complexes have been characterized in solution by NMR spectroscopy, demonstrating rapid ligand exchange at ambient temperature for rare earth complexes, and slow exchange on the NMR timescale for complexes of Al; in all cases the mer-isomer is observed exclusively. Crystal structures are reported for [YL3] 2 (L = (S)-2-(4-isopropyl-4,5-dihydrooxazol-2-yl)phenolate), mer-[YbL3] (L = (S)-2-(4-isopropyl-4,5-dihydrooxazol-2-yl)-6-methylphenolate) and mer-[AlL3] (L = (S)-2-(4-isopropyl-4,5-dihydrooxazol-2-yl)-6-methylphenolate, L = (S)-2-(4-isopropyl-4,5-dihydrooxazol- 2-yl)-6-cyanophenolate), L = (S)-1-(4-isopropyl-4,5-dihydrooxazol-2-yl) naphthalen-2-olate, L = 1-(4,4-dimethyl- 4,5-dihydrooxazol-2-yl)naphthalen-2-olate).