Bis(pyrazolylethyl) ether ligation to zinc and cobalt: Meridional vs facial coordination and the suitability of such ligands in providing a NNO donor set for modeling bioinorganic aspects of zinc chemistry

Bis(pyrazolylethyl) ether ligation to zinc and cobalt: Meridional vs facial coordination and the suitability of such ligands in providing a NNO donor set for modeling bioinorganic aspects of zinc chemistry
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DOI:
10.1021/ic9512744
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发表时间:
1996-04-24
影响因子:
4.6
通讯作者:
Parkin, G
Parkin, G
中科院分区:
化学2区
文献类型:
--
作者:
Dowling, C;Murphy, VJ;Parkin, G

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锌和钴的双(吡唑基乙基)醚衍生物,即[eta(3)-O(CH(2)CH(2)pz(Pri 2))(2)]Zn(NO3)(2)和[eta(3)-O(CH(2)CH(2)PzMe(2))(2)]CO(NO3)(2)的结构已被确定,目的是解决此类配体在模拟锌化学的生物无机方面的适用性。具体考虑的可能性,双(吡唑基乙基)醚配体可以提供一个NNO供体系统,可以模拟锌的结合方面的酶,如嗜热菌蛋白酶的蛋白质骨架。结构的研究表明,双(吡唑基乙基)醚配体确实协调通过其每个NNO功能,但酶的关系是有限的,而不是面部的协调几何结构的通过。[eta(3)-O(CH(2)CH(2)Pz(Pri 2))(2)]Zn(NO3)(2)为单斜晶系,P2(1)/c(No.14),a = 11.619(2)埃,B = 14.380(3)埃,c = 16.757(2)埃,β = 90.44(2)度,Z = 4。[eta(3)-O(CH(2)CH(2)pz(Me 2))(2)]Co(NO3)(2)为单斜晶系,C2/c(No.15),a = 17.136(3)埃,B = 10.505(2)埃,c = 11.121(2)埃,β = 104.62(3)度,Z = 4。
The structures of bis(pyrazolylethyl) ether derivatives of zinc and cobalt, namely [eta(3)-O(CH(2)CH(2)pz(Pri2))(2)]Zn(NO3)(2) and [eta(3)-O(CH(2)CH(2)PzMe(2))(2)]CO(NO3)(2), have been determined with a view to addressing the applicability of such ligands in modeling bioinorganic aspects of zinc chemistry. Specific consideration is given to the possibility that bis(pyrazolylethyl) ether ligands may provide an NNO donor system which may model aspects of the binding of zinc to protein backbones in enzymes such as thermolysin. The structural studies demonstrate that the bis(pyrazolylethyl) ether ligands do indeed coordinate via each of their NNO functionalities but that the relationship to the enzyme is limited by the adoption of meridional rather than facial coordination geometries. [eta(3)-O(CH(2)CH(2)Pz(Pri2))(2)]Zn(NO3)(2) is monoclinic, P2(1)/c (No. 14), with a = 11.619(2) Angstrom, b = 14.380(3) Angstrom, c = 16.757(2) Angstrom, beta = 90.44(2)degrees, and Z = 4. [eta(3)-O(CH(2)CH(2)pz(Me2))(2)]Co(NO3)(2) is monoclinic, C2/c (No. 15), with a = 17.136(3) Angstrom, b = 10.505(2) Angstrom, c = 11.121(2) Angstrom, beta = 104.62(3)degrees, and Z = 4.