ZINC-COMPLEXES OF THE LIGAND DIPICOLYLGLYCINE
ZINC-COMPLEXES OF THE LIGAND DIPICOLYLGLYCINE
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DOI：
10.1021/ic00112a038
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发表时间：
1995-04-12
影响因子：
4.6
通讯作者：
VAHRENKAMP, H
中科院分区：
文献类型：
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作者：
ABUFARAG, A;VAHRENKAMP, H
N，N-二(2-picolyl - >甘氨酸（L-H）非游离态通过其乙酯（L-Et）引入锌配合物中，生成中间配合物（L-Et）ZnBr2(1)、（L-Et）Zn(NO3)(2)(2)和（L-Et）(2)Zn(ClO4)2。水(3)。在水的存在下，自催化水解将2转化为[L]。锌(H2O)(2)] 3号。水(4)与八面体和3成三聚体[L]。锌ClO4。H2O(5)与锌在固态下的三角-双锥体配位。5被发现是一个很好的起始材料，用于引入共配体，形成类似锌在具有N，N，O供体的酶中的配位的配合物。Zn(Im)(H2O)]ClO4(6)与2-甲基咪唑合成三角-双锥体配合物[L]。Zn(MeIm)]ClO4(7)，与磷酸二苯酯形成三角-双锥体配合物[L]。锌(磷酸盐)]。2 h (2) O(8)。通过x射线工作证实了1和4-8在固态中的配位。核磁共振研究（固态和溶液）和电导率测量揭示了溶液中解离和溶剂化的各种状态，其中三角-双锥体阳离子[L。Zn(H2O]（+）可能是所有水平衡的共同和主要成分。
N,N-bis(2-picolyl>glycine (L-H) which was not obtained in the free state was introduced into zinc complexes via its ethyl ester (L-Et) which yielded the intermediate complexes (L-Et)ZnBr2 (1), (L-Et)Zn(NO3)(2) (2), and (L-Et)(2)Zn(ClO4)2 . H2O (3). Autocatalytic hydrolysis in the presence of water turned 2 into [L . Zn(H2O)(2)]NO3 . H2O (4) with an octahedral and 3 into trimeric [L . Zn]ClO4 . H2O (5) with a trigonal-bipyramidal coordination of zinc in the solid state. 5 was found to be a good starting material for the introduction of coligands forming complexes that mimic the coordination of zinc in enzymes with a N,N,O donor set: With imidazole the octahedral complex [L . Zn(Im)(H2O)]ClO4 (6) was obtained, with 2-methylimidazole the trigonal-bipyramidal complex [L . Zn(MeIm)]ClO4 (7), and with diphenyl phosphate the trigonal-bipyramidal complex [L . Zn(Phos)]. 2H(2)O (8). The coordination in the solid state was confirmed for 1 and 4-8 by X-ray work. NMR studies (solid state and solution) and conductivity measurements have revealed various states of dissociation and solvation in solution, with the trigonal-bipyramidal cation [L . Zn(H2O](+) probably being a common and major constituent of all aqueous equilibria.