...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >A dinuclear [{(p-cym)(RuCl)-Cl-II}(2)(mu-bpytz(center dot-))](+) complex bridged by a radical anion: synthesis, spectroelectrochemical, EPR and theoretical investigation (bpytz=3,6-bis(3,5-dimethylpyrazolyl)1,2,4,5-tetrazine; p-cym = p-cymene)
【24h】

A dinuclear [{(p-cym)(RuCl)-Cl-II}(2)(mu-bpytz(center dot-))](+) complex bridged by a radical anion: synthesis, spectroelectrochemical, EPR and theoretical investigation (bpytz=3,6-bis(3,5-dimethylpyrazolyl)1,2,4,5-tetrazine; p-cym = p-cymene)

机译：由自由基阴离子桥接的双核[{（p-cym）（RuCl）-Cl-II}（2）（μ-bpytz（中心点-））（+）络合物：合成，光谱电化学，EPR和理论研究（ bpytz = 3,6-双（3,5-二甲基吡唑基）1,2,4,5-四嗪;对-cym =对-异丙基）

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

The reaction of the chloro-bridged dimeric precursor [{(p-cym) (RuCl)-Cl-II}(mu-Cl)](2) (p-cym = p-cymene) with the bridging ligand 3,6-bis(3,5-dimethylpyrazolyl)-1,2,4,5-tetrazine (bpytz) in ethanol results in the formation of the dinuclear complex [{(p-cym) (RuCl)-Cl-II} 2(mu-bpytz(center dot-))](+), [1](+). The bridging tetrazine ligand is reduced to the anion radical (bpytz(center dot-)) which connects the two Ru-II centres. Compound [1](PF6) has been characterised by an array of spectroscopic and electrochemical techniques. The radical anion character has been confirmed by magnetic moment (corresponding to one electron paramagnetism) measurement, EPR spectroscopic investigation (tetrazine radical anion based EPR spectrum) as well as density functional theory based calculations. Complex [1](+) displays two successive one electron oxidation processes at 0.66 and 1.56 V versus Ag/AgCl which can be attributed to [{(p-cym) (RuC)-C-II}(2)(mu-bpytz(center dot-))](+)/[{(p-cym) (RuCl)-Cl-II}(2)(mu-bpytz)](2+) and [{(p-cym) (RuCl)-Cl-II}(2)(mu-bpytz)](+)/[{(p-cym) (RuICl)-I-II}(2)(mu-bpytz)](2+) processes (couples I and (II)), respectively. The reduction processes (couple (III)-couple V), which are irreversible, likely involve the successive reduction of the bridging ligand and the metal centres together with loss of the coordinated chloride ligands. UV-Vis-NIR spectroelectrochemical investigation reveals typical tetrazine radical anion containing bands for [1](+) and a strong absorption in the visible region for the oxidized form [1](2+), which can be assigned to a Ru-II -> pi* (tetrazine) MLCT transition. The assignment of spectroscopic bands was confirmed by theoretical calculations.
机译：氯桥联的二聚体前体[{（p-cym）（RuCl）-Cl-II}（mu-Cl）]（2）（p-cym =对-甲基异丙基苯）与桥连配体3,6-的反应乙醇中的双（3,5-二甲基吡唑基）-1,2,4,5-四嗪（bpytz）导致双核络合物[{（p-cym）（RuCl）-Cl-II} 2（mu- bpytz（中心点-））]（+），[1]（+）。桥接的四嗪配体被还原为连接两个Ru-II中心的阴离子基团（bpytz（中心点-））。化合物[1]（PF6）已通过一系列光谱学和电化学技术进行了表征。自由基阴离子的特性已经通过磁矩（对应于一个电子顺磁性）测量，EPR光谱研究（基于四嗪自由基阴离子的EPR光谱）以及基于密度泛函理论的计算得到了证实。复合物[1]（+）在0.66和1.56 V的电压下相对于Ag / AgCl表现出两个连续的单电子氧化过程，这可以归因于[{（p-cym）（RuC）-C-II}（2）（mu-bpytz （中心点-））]（+）/ [{（对-cym）（RuCl）-Cl-II}（2）（μ-bpytz）]（2+）和[{（对-cym）（RuCl） -Cl-II}（2）（mu-bpytz）]（+）/ [{{（p-cym）（RuICl）-I-II}（2）（mu-bpytz）]（2+）过程（对I和（II））。不可逆的还原过程（对（III）-对V）可能涉及桥连配体和金属中心的连续还原以及配位氯配体的损失。 UV-Vis-NIR光谱电化学研究表明，典型的四嗪自由基阴离子包含[1]（+）的谱带，并且在可见光区域对氧化形式[1]（2+）具有强吸收，可以将其分配给Ru-II -> pi *（四嗪）MLCT转换。通过理论计算确认了光谱带的分配。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号