Development of Electrical Conductors with Multi-dimensionality Based on Non-planar Metal Complexes with Sulfur-rich Ligands as an Extended pi-System

基于富硫配体非平面金属配合物作为扩展 pi 系统的多维导电体的开发

• 批准号: 09640665
• 负责人: MATSUBAYASHI Gen-etsu
• 金额: $ 1.98万
• 依托单位: Oasaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640665/
• 关键词: Dithiolate complex; Molybdenum complex; Platinum complex; Cobalt complex; Titanium complex; Ruthenium complex; Oxidation; Electrical conductivity; シクロペンタジエニル錯体; スズ錯体; 酸化還元電位

Various metal complexes with dithiolato ligands containing many sulfur atoms asan extended it-system have been synthesized, and by the oxidation of them new electrical conductors have been obtained and their properties c1arified.[NEt_4]_2[Mo(O)(etdt)_2](etdt=C_8H_4S_4^<2->) having five-coordinate square-pyramid geometry has been prepared. The oxidized species [NEt_4]_<0.3>[Mo(O)(etdt)_2] and [Fe(C_5Me_5)_2]_<0.05>[Mo(O)(etdt)_2] exhibited high electrical conduc-tivities (0.29 and 5.9 S cm^<-1>, respectively, at room temperature for compacted pellets). In the oxidized species S-S interactions among the etdt-ligand moieties form effective electron-conduction pathways.Co(III)- and Ti(IV)- complexes having cyclopentadienyl groups and dmit (C_3S_5^<2->) or etdt ligand have been investigated.Oxidation behavior of reactions of Co (L) (dmit) (L = eta^5-C_5H_5, eta^5-C_5Me_5) with bromine and the crystal structure of the one-electron oxidized species Co(eta^5-C_5Me_5)(dmit)Br have been clarifie … More d, together with a strong antiferromagnetic interaction between the oxidized dmit-ligand moieties.Co(eta^5-C_5H_5)(etdt) and Ti(eta^5-C_5H_5)_2(etdt) have been synthesized and properties of their oxidized complexes studied. Especially, [Co(eta^5-C_5H_5)(etdt)] I_3 and [Co(eta^5-C_5H_5)(etdt)][PF_6]_<0.7> exhibited high electrical conductivities of 0.19 and 0.16 S cm^<-1>,respectively, at room temperature measured for compacted pellets.Electrical conductivities of oxidized species of dmit- and etdt-Ru(II) cpmplexes have been studied. Ru(bpy)_2(dmit) and Ru(bpy)_2(etdt) (bpy = 2,2'-bipyridine) having a bulky six-coordinate geometry have been synthesized. The oxidized species obtained by reactions with iodine, Ru(bpy)_2(etdt)] I and Ru(bpy)_2(etdt)] (I_3)_<2.1>, have electrical conductivities of 7.4 x 10^<-7> and 7.0 x 10^<-4> S cm^<-1>, respectively. Even in the highly bulky complexes coordinated with two bpy ligands, extended oxidation on the etdt-ligand moiety leads to effective molecular interaction through S-S contacts among etdt-Iigand moieties. Less

合成了多种含硫二硫配体的金属络合物作为一个扩展的体系，通过它们的氧化得到了新的导电体，并制备了具有五坐标方锥构型的性能c1arified.[NEt_4]_2[Mo(O)(etdt)_2](etdt=C_8H_4S_4^&lt；2-&gt；)。氧化物种[Net_4]_(0.3&gt；[Mo(O)(Etdt)_2]和[Fe(C_5Me_5)_2]_(0.05&gt；[Mo(O)(Etdt)_2])具有较高的电导率(室温下致密球团的电导率分别为0.29和5.9 S cm)。在被氧化物种中，S-S配体之间的相互作用形成了有效的电子传导途径。本文研究了含环戊二烯基的Co(Ⅲ)和Ti(IV)与dMIT(C_3S_5^&lt；2-&gt；)或eTdt配体的反应。阐明了Co(L)(DMIT)(L=ETA^5-C5H5，ETA^5-C5Me_5)与溴反应的氧化行为和单电子被氧化物种Co(ETA^5-C5Me_5)(DMIT)的晶体结构Co(eta^5-C_5H_5)(Etdt)和Ti(eta^5-C_5H_5)_2(Etdt)，并研究了它们的氧化配合物的性质。特别是[Co(eta^5-C_5H_5)(Etdt)]I_3和[Co(eta^5-C_5H_5)(Etdt)][PF_6]和[Co(eta^5-C_5H_5)(Etdt)][PF_6]和[Co(eta^5-C_5H_5)(Etdt)][PF_6]和[Co(eta^5-C_5H_5)(Etdt)][PF_6]和[Co(eta^5-C_5H_5)(Etdt)][PF_6]和[Co(eta^5-C_5H_5)(Etdt)][PF_6]和[Co(eta^5-C_5H_5)(Etdt)][PF_6]和[Co(eta^5-C_5H_5)(Etdt)][PF_6]和[Co(eta^5-C_5H_5)(Etdt)][PF_6]_合成了六配位体型的Ru(Bpy)_2(Dmit)和Ru(Bpy)_2(Etdt)(bpy=2，2‘-联吡啶)。与碘反应得到的氧化物种Ru(Bpy)_2(Etdt)]i和Ru(Bpy)_2(Etdt)](I_3)_(2.1&gt；)的电导率分别为7.4x10^&lt；-7&gt；和7.0×10^&lt；-4&gt；S cm^&lt；即使在与两个bpy配体配位的高体积配合物中，etdt配体部分上的扩大氧化也通过etdt配体部分之间的S-S接触而导致有效的分子相互作用。较少

项目成果

中野元裕: "Preparation and properities of C_8H_4S_8-platinum (II) complexes and electrical conductivities of their oxidized species and X-ray crystal structure of C_8H_4S_8 (CH_2CH_2CN) _2 as a pro-ligand compound" Inorganica Chimica Acta. (印刷中).

Motohiro Nakano：“C_8H_4S_8-铂 (II) 配合物的制备和性质及其氧化物质的电导率以及作为配体化合物的 C_8H_4S_8 (CH_2CH_2CN) _2 的 X 射线晶体结构”Inorganica Chimica Acta（正在出版）。

H.Mori, M.Nakano, H.Tamura, and G.Matsubayashi: "Oxidation Properties of Co (eta^5-C_5H_5) - (C_8H_4S_8) and CoL (C_3S_5) (L=eta^5-C_5H_5and eta^5-C_5Me_5) and Crystal Structure of Co(eta^5-C_5H_5) (C_3S_5) Br." J.Organomet.Chem.574-No.1. 77-85 (1999)

H.Mori、M.Nakano、H.Tamura 和 G.Matsubayashi：“Co (eta^5-C_5H_5) - (C_8H_4S_8) 和 CoL (C_3S_5) 的氧化性质（L=eta^5-C_5H_5 和 eta^5-

森 博之: "Oxidation Properties of Co(η^5-C_5H_5)(C_8H_4S_8)and CoL(C_3S_5)(L=η^5-C_5H_5 and η^5-C_5Me_5)and C_8H_4S_8^<2->)and crystal structur of Co(η^5-C_5H_5)(C_3S_5)Br," Journal of Organometallic Chemistry. 574・1. 77-85 (1999)

Hiroyuki Mori：“Co(η^5-C_5H_5)(C_8H_4S_8)和CoL(C_3S_5)(L=η^5-C_5H_5和η^5-C_5Me_5)和C_8H_4S_8^<2->)的氧化性质和晶体结构Co(η^5-C_5H_5)(C_3S_5)Br，《有机金属化学杂志》. 574・1. 77-85 (1999)

H.Mori, M.Nakano, H.Tamura, G.Matsubayashi, and W.Mori: "Paramagnetic Organocobalt (III) Dithiolate Complex : Crystal Structure and Magnetic Property ofCo (eta^5-C_5Me_5) (C_3S_5) Br." Chem.Lett.No.8. 729-730 (1998)

H.Mori、M.Nakano、H.Tamura、G.Matsubayashi 和 W.Mori：“顺磁性有机钴 (III) 二硫醇络合物：Co (eta^5-C_5Me_5) (C_3S_5) Br 的晶体结构和磁性。”

中野元裕: "Preparation and properties of C_8H_4S_8-platinum(II)complexes and electrical conductivities of their oxidized species and X-ray crystal structure of C_8H_4S_8(CH_2CH_2CN)_2 as a pro-ligand compound" Inorganica Chimica Acta. 279・1. 165-171 (1998)

Motohiro Nakano：“C_8H_4S_8-铂(II)配合物的制备和性质及其氧化物质的电导率以及作为前配体化合物的C_8H_4S_8(CH_2CH_2CN)_2的X射线晶体结构”Inorganica Chimica Acta 279・1。 -171 (1998)