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Group 12 Metal Complexes of an 18-Membered N2O2S2 Macrocycle Incorporating Two Pyridines: First Examples of an Infinite Mercury(I) Complex and a Dumbbell-Shaped Heteronuclear Complex with a Macrocyclic Ligand
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2016-10-20 00:00:00 , DOI: 10.1021/acs.inorgchem.6b01583
Sujin Seo 1 , Huiyeong Ju 1 , Seulgi Kim 1 , In-Hyeok Park 1 , Eunji Lee 1 , Shim Sung Lee 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2016-10-20 00:00:00 , DOI: 10.1021/acs.inorgchem.6b01583
Sujin Seo 1 , Huiyeong Ju 1 , Seulgi Kim 1 , In-Hyeok Park 1 , Eunji Lee 1 , Shim Sung Lee 1
Affiliation
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Homo- and heteronuclear group 12 metal (Zn2+, Cd2+, and Hg2+) complexes 1–6 containing a newly designed 18-membered N2O2S2 macrocycle incorporating two pyridine subunits (L) were prepared and structurally characterized. The individual complexes isolated exhibit unusual stoichiometries, geometries, oxidation states, and structural topologies and include an infinite mercurous complex and a heteronuclear dumbbell-shaped complex. Both the Zn(II) complex [Zn(L)][ZnBr4] (1) and the Cd(II) complex [Cd(L)Br2] (2) are mononuclear, with the metal ion located inside the macrocyclic cavity. The six-coordinated Zn(II) center in 1 adopts an octahedral geometry and is shielded from the anion and solvent by the strongly bound macrocycle. The Cd(II) center in 2 is seven-coordinate, being bound equatorially to two N donors, two O donors, and a S donor from the macrocycle and axially to two bromide ions on opposite sides of the macrocyclic plane, adopting a pentagonal-bipyramidal geometry. In the Hg(II) complexations, the configuration adopted by the macrocycle L shows a dependence of the nuclearity on the anion used. When mercury(II) bromide was used, the dinuclear complex [HgII2(L)Br4] (3) was obtained, while the reaction with mercury(II) nitrate afforded the unexpected Hg(I) complex {[HgI2(L)](NO3)2}n (4) with a one-dimensional polymeric structure. In heterometallic complexation experiments, one-pot reaction of L with a mixture of ZnBr2 and CdBr2·4H2O resulted in the stepwise isolation of two pure solubility-dependent Cd(II) complexes (2 and 5), including the half-dumbbell-type complex [Cd(L)(μ-Br)(CdBr3)] (5), while a mixture of CdBr2·4H2O and HgBr2 yielded the heterometallic bis(macrocycle) product [(CdL)2(μ-Hg2Br6)](Hg2Br6) (6). This is the first example of a heteronuclear dumbbell-shaped complex in which two terminal macrocyclic Cd(II) complexes are linked by a hexabromodimercury(II) cluster via Cd–Br–Hg bonds. The heterometallic dumbbell 6 can be considered as a good example of competition and collaboration between Cd(II) and Hg(II) ions because its formation is associated with the higher coordination affinity of Cd(II) toward the macrocycle and the formation of the (Hg2Br6)2– cluster, which links the two endocyclic Cd(II) complexes directly. Both NMR titration and comparative NMR data indicate a relatively higher coordination affinity of Cd(II) toward the macrocycle than occurs for Hg(II), in parallel to the situation observed in the solid state.
中文翻译:
带有两个吡啶的18元N 2 O 2 S 2大环化合物的第12组金属配合物:无限汞(I)配合物和哑铃形异核配合物与大环配体的第一个例子
均聚物和异核第12族金属(锌2+,镉2+和Hg 2+)络合物1 - 6含有一个新设计的18元N- 2 ö 2 š 2大环装有二吡啶亚基(大号制备和结构)表征。分离出的单个复合物表现出不同寻常的化学计量,几何形状,氧化态和结构拓扑,并且包括无限量的汞复合物和异核哑铃状复合物。Zn(II)络合物[Zn(L)] [ZnBr 4 ](1)和Cd(II)络合物[Cd(L)Br2 ](2)是单核的,金属离子位于大环腔内。在六配位的Zn(II)中心1采用的八面体几何形状,并从阴离子和溶剂通过强结合大环屏蔽。在CD(II)中心2是七坐标,被平展结合于两个N供体,两个O供体,和从大环A S供体和大环平面的相对侧沿轴向两个溴离子,采用pentagonal-双锥体的几何形状。在Hg(II)络合物中,大环L所采用的构型显示出核原子对所用阴离子的依赖性。当使用溴化汞(II)时,双核络合物[Hg II 2(L)Br 4 ](3),而与硝酸汞(II)的反应得到了意想不到的Hg(I)络合物{[Hg I 2(L)](NO 3)2 } n(4),其中一尺寸聚合物结构。在异金属络合实验中,L与ZnBr 2和CdBr 2 ·4H 2 O的混合物进行一锅法反应导致逐步分离出两种依赖溶解度的纯Cd(II)配合物(2和5),包括半哑铃型复合物[Cd(L)(μ-Br)(CdBr3)](5),而CDBR的混合物2 ·4H 2 O和HgBr 2,产生杂金属双(大环)产物[(CD大号)2(μ-汞柱2溴6)](汞柱2溴6)(6)。这是异核哑铃状复合物的第一个例子,其中两个末端大环Cd(II)配合物通过Cd-Br-Hg键通过六溴二汞(II)簇连接。杂金属哑铃6可以看作是竞争与合作的典范Cd(II)和Hg(II)离子之间的相互作用,因为其形成与Cd(II)对大环的更高配位亲和力以及(Hg 2 Br 6)2–簇的形成有关,该簇连接两个环内Cd (二)直接配合。NMR滴定和比较NMR数据均表明Cd(II)对大环的配位亲和力比Hg(II)高,与在固态下观察到的情况平行。
更新日期:2016-10-20
中文翻译:
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带有两个吡啶的18元N 2 O 2 S 2大环化合物的第12组金属配合物:无限汞(I)配合物和哑铃形异核配合物与大环配体的第一个例子
均聚物和异核第12族金属(锌2+,镉2+和Hg 2+)络合物1 - 6含有一个新设计的18元N- 2 ö 2 š 2大环装有二吡啶亚基(大号制备和结构)表征。分离出的单个复合物表现出不同寻常的化学计量,几何形状,氧化态和结构拓扑,并且包括无限量的汞复合物和异核哑铃状复合物。Zn(II)络合物[Zn(L)] [ZnBr 4 ](1)和Cd(II)络合物[Cd(L)Br2 ](2)是单核的,金属离子位于大环腔内。在六配位的Zn(II)中心1采用的八面体几何形状,并从阴离子和溶剂通过强结合大环屏蔽。在CD(II)中心2是七坐标,被平展结合于两个N供体,两个O供体,和从大环A S供体和大环平面的相对侧沿轴向两个溴离子,采用pentagonal-双锥体的几何形状。在Hg(II)络合物中,大环L所采用的构型显示出核原子对所用阴离子的依赖性。当使用溴化汞(II)时,双核络合物[Hg II 2(L)Br 4 ](3),而与硝酸汞(II)的反应得到了意想不到的Hg(I)络合物{[Hg I 2(L)](NO 3)2 } n(4),其中一尺寸聚合物结构。在异金属络合实验中,L与ZnBr 2和CdBr 2 ·4H 2 O的混合物进行一锅法反应导致逐步分离出两种依赖溶解度的纯Cd(II)配合物(2和5),包括半哑铃型复合物[Cd(L)(μ-Br)(CdBr3)](5),而CDBR的混合物2 ·4H 2 O和HgBr 2,产生杂金属双(大环)产物[(CD大号)2(μ-汞柱2溴6)](汞柱2溴6)(6)。这是异核哑铃状复合物的第一个例子,其中两个末端大环Cd(II)配合物通过Cd-Br-Hg键通过六溴二汞(II)簇连接。杂金属哑铃6可以看作是竞争与合作的典范Cd(II)和Hg(II)离子之间的相互作用,因为其形成与Cd(II)对大环的更高配位亲和力以及(Hg 2 Br 6)2–簇的形成有关,该簇连接两个环内Cd (二)直接配合。NMR滴定和比较NMR数据均表明Cd(II)对大环的配位亲和力比Hg(II)高,与在固态下观察到的情况平行。