Design and synthesis of copper complexes of novel ligands based on the pyridine thiolate group

isamu Kinoshita; L.james Wright; Sachiko Kubo; Kentaro Kimura; Akio Sakata; Toshihiro Yano; takanori Nishioka; Kiyoshi Isobe

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Design and synthesis of copper complexes of novel ligands based on the pyridine thiolate group

机译：基于吡啶硫醇盐基团的新型配体铜配合物的设计与合成

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The versatile coordination properties of 2,2'-dipyridyldisulfide (dpds)enables a series of different copper complexes to be isolated in good yield,including [CuCl_2(mu-dpds)](1) which has a one-dimensional helical structure and [Cu(mu-Cl)(mu-dpds)](4) which has a two-dimentsional sheet structure.Flexible movement of the disulfide group in the dpds ligand facilitates the formatio of complexes with a diverse range of structures.Compound 1 transforms into 4 almost quantitatively on standing in contact with methanol.After prolonged standing 4 slowly converts to the stable,betain-contaning product,[Cu(mu-1-(2-pyridine)pyridiniumthiolato)(mu-Cl)](8) with the concomitant production of elemental sulfur.The bromide congener of 4 undergoes the same transfromation.the free ligand,1-(2-pyridine)pyridiniumthiolate,can be released from 8by treatment with CN~-.On treatment of bis(2-pyridyl-thio)methane (BPTM) with CuCl_2[CuCl_2(BPTM)]_n(9) is formed.This complex has an infinite helical chain structure.Reaction between tris(2-pyridylthio)methane (TPTMH) and CuBr gave [CuBr(TPTM)](12) and with [Cu(NCCH_3)_4]PF_6 in the presence of oxygen,the complex[Cu(CH_3CN)(TPTM)]PF_6(14) is formed.complex 14 is the first structurally characterised example of a complex containing a Cu(II)-C(sp~3) bond.

机译：2,2'-二吡啶基二硫化物（dpds）的通用配位特性使一系列不同的铜络合物能够以高收率分离，包括具有一维螺旋结构的[CuCl_2（mu-dpds）]（1）和[具有二维片状结构的Cu（mu-Cl）（mu-dpds）]（4）。dpds配体中二硫键的灵活移动促进了结构多样的配合物的形成。化合物1转变为4与甲醇接触时几乎定量。长时间放置后4缓慢转化为稳定的，含甜菜碱的产物[Cu（mu-1-（2-吡啶）吡啶硫醇吡啶鎓）（mu-Cl）]（8），伴随产生元素硫.4的溴同系物经历相同的转化。通过用CN〜-处理可以从8中释放出游离配体1-（2-吡啶）吡啶硫醇盐。形成具有CuCl_2 [CuCl_2（BPTM）] _ n（9）的甲烷（BPTM）。该配合物具有无限的螺旋链结构e。在氧气存在下，三（2-吡啶硫基）甲烷（TPTMH）与CuBr之间的反应生成[CuBr（TPTM）]（12）并与[Cu（NCCH_3）_4] PF_6形成络合物[Cu（CH_3CN）（形成TPTM）] PF_6（14）。配合物14是包含Cu（II）-C（sp-3）键的配合物的第一个结构表征的实例。

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《Dalton transactions: An international journal of inorganic chemistry》 |2003年第10期|共11页
作者
isamu Kinoshita; L.james Wright; Sachiko Kubo; Kentaro Kimura; Akio Sakata; Toshihiro Yano; takanori Nishioka; Kiyoshi Isobe;
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1. Design and synthesis of copper complexes of novel ligands based on the pyridine thiolate group [J] . isamu Kinoshita, L.james Wright, Sachiko Kubo, Dalton transactions: An international journal of inorganic chemistry . 2003,第10期

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6. Synthesis and Ligand Non-Innocence of Thiolate-Ligated (N4S) Iron(II) and Nickel(II) Bis(imino)pyridine Complexes [O] . Leland R. Widger, Yunbo Jiang, Maxime Siegler, -1

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机译：硫醇盐连接（N4s）铁（II）和镍（II）双（亚氨基）吡啶配合物的合成和配体非天然

Design and synthesis of copper complexes of novel ligands based on the pyridine thiolate group

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