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首页> 外文期刊>Bulletin of the Chemical Society of Japan >Tetra-and Di-Nuclear Copper(II)Complexes with Stereoisomers of Sulfinylcalix[4]arene Arising from the Disposition of Four S=O Groups
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Tetra-and Di-Nuclear Copper(II)Complexes with Stereoisomers of Sulfinylcalix[4]arene Arising from the Disposition of Four S=O Groups

机译：由四个S = O基团的分布形成的亚砜基杯[4]芳烃的立体异构体的四核和二核铜（II）配合物

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A systematic investigation was conducted on the structures of tetra-and di-nuclear copper(II)complexes with three stereoisomers of sulfinylcalix[4]arenes(H4L),the isomerism of which is determined by the disposition of the sulfinyl oxygen with respect to a reference oxygen from the mean plane containing four sulfur atoms.The sulfmylcalix[4]arene with a trans-cis-trans S=O orientation(H_4L~(rtct))reacted with Cu(OAc)2 to form [Cu_4~(II)(L~(rtct))(OAc)_3(mu-MeO)(MeOH)](1),in which L~(rtct4-)adopts a cone conformation to afford tetrakis fac-tridentate coordination through four phenoxo oxygens and four sulfinyl groups giving a square Cu_4~(II)core.Ligands H_4L~(rccc)and H_4L~(rctt)having cis-cis-cis and cis-trans-trans configurations formed [CU_4~(II)(L~(rccc))(OAc)_3(mu-OH)](2)and [Cu_4~(II)(L~(rctt))(OAc)_3(mu-OH)](3),respectively,which have common features,such as a cone-type conformation of L~(4-),tetrakis fac-tridentate coordination fashion,and tetra-copper(II)core in a square-pyramidal geometry.The similarities among 1-3 clearly show that sulfmylcalix[4]arenes can coordinate to Cu~(II)in a fac-tridentate fashion via a donor atom X(O or S)from a sulfinyl group and two flanking phenoxo 0~-s and that X is simply determined by the X-Cu distance.Using [Cu(acac)2] as a copper(II)source,H_4L~(rctt)formed [Cu_2~(II)(H_2L~(rett))_2](4),suggesting the significance of auxiliary ligand for bridging copper(II)centers to assemble the core,that is,the acetato ligands in complexes 1-3 are needed to form the core structure.Metal-metal interactions were investigated by means of magnetic susceptibility,and it was found that both ferro-and antiferromagnetic interactions occur in tetracopper(II)complex 3.In contrast,antiferromagnetic interaction is present in dicopper(II)complex 4.
机译：对具有亚砜基杯[4]芳烃（H4L）的三种立体异构体的四核和二核铜（II）配合物的结构进行了系统的研究，其异构体由亚磺酰基氧相对于α的位置决定。含四个硫原子的平均平面中的参考氧。具有反式-顺式-反式S = O取向（H_4L〜（rtct））的亚磺酰基杯[4]芳烃与Cu（OAc）2反应形成[Cu_4〜（II） （L〜（rtct））（OAc）_3（mu-MeO）（MeOH）]（1），其中L〜（rtct4-）采用圆锥构象，通过四个苯氧和四个亚磺酰基提供四原子三齿配位H_4L〜（rccc）和H_4L〜（rctt）具有顺-顺-顺和顺-反-反式构型的配体H_4L〜（rccc）和形成的[CU_4〜（II）（L〜（rccc）） （OAc）_3（mu-OH）]（2）和[Cu_4〜（II）（L〜（rctt））（OAc）_3（mu-OH）]（3）分别具有共同的特征，例如L〜（4-）的锥型构象，四面体-三齿配位方式，四角锥体中的四铜（II）核1-3之间的相似性清楚地表明，亚磺酰基杯[4]芳烃可以通过亚磺酰基和两个侧基酚氧的供体原子X（O或S）以三三齿形式与Cu〜（II）配位。 〜-s并且X可以简单地由X-Cu距离决定。使用[Cu（acac）2]作为铜（II）源，H_4L〜（rctt）形成[Cu_2〜（II）（H_2L〜（rett）） ）_2]（4），表明辅助配体对于桥接铜（II）中心组装核的意义，即需要配合物1-3中的乙酰基配体形成核结构。研究了金属与金属的相互作用通过磁化率，发现四铜（II）配合物3中同时发生铁磁性和反铁磁相互作用。相反，双铜（II）配合物4中存在反铁磁性相互作用。

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