...
  • 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 >Cyclopentadienyl chromium diimine, pyridine-imine complexes: Ligand-based radicals, metal-based redox chemistry
【24h】

Cyclopentadienyl chromium diimine, pyridine-imine complexes: Ligand-based radicals, metal-based redox chemistry

机译：环戊二烯基铬二亚胺，吡啶-亚胺络合物：基于配体的自由基，基于金属的氧化还原化学

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

Paramagnetic CpCr(iii) complexes with antiferromagnetically-coupled anionic radical diimine and pyridine-imine ligands were prepared and characterized. The diimine chloro CpCr[(ArNCR) _2]Cl complexes (1: Ar = 2,6-iPr _2C _6H _3 (Dpp), R = H; 2: Ar = 2,6-Me _2C _6H _3 (Xyl), R = Me; 3: Ar = 2,4,6-Me _3C _6H _2 (Mes), R = Me) were synthesized by treatment of previously reported Cr(diimine)(THF) _2Cl _2 precursors with NaCp. Reduction of 1 with Zn gives CpCr[(DppNCH) _2], 4, resulting from reduction of Cr(iii) to Cr(ii) with retention of the ligand-based radical. Alkoxide complexes CpCr[(DppNCH) _2](OCR _2R′) (5: R = Me, R′ = Ph; 6: R = iPr, R′ = H) were synthesized by protonolysis of Cp _2Cr with HOCR _2R′ in the presence of the neutral diimine and catalytic base. The corresponding radical pyridine-imine complexes CpCr(PyCHNMes)Cl (9), CpCr(PyCHNMes) (8), and CpCr(PyCHNMes)(OCMe _2Ph) (11), were prepared by analogous routes. Oxidation of 8 with iodine gives CpCr(PyCHNMes)I (10) where oxidation of Cr(ii) to Cr(iii) again occurs with retention of the anionic pyridine-imine radical ligand. The molecular structures of complexes 1, 2, 4-8, 10 and 11 were determined by single-crystal X-ray diffraction. Unusual low energy bands were observed in the UV-vis spectra of the reported complexes, with particularly strong transitions observed for the Cr(ii) complexes 4 and 8. The electronic structure of pyridine-imine complexes 8 and 10 were investigated by theoretical calculations.
机译：制备并表征了具有反铁磁耦合阴离子自由基二亚胺和吡啶-亚胺配体的顺磁性CpCr（iii）配合物。二亚胺氯CpCr [（ArNCR）_2] Cl络合物（1：Ar = 2,6-iPr _2C _6H _3（Dpp），R = H; 2：Ar = 2,6-Me _2C _6H _3（Xyl），R ＝ Me; 3：Ar ＝ 2,4,6-Me _3C _6H _2（Mes，R = Me）是通过用NaCp处理先前报道的Cr（diimine）（THF）_2Cl _2前体合成的。用Zn还原1得到CpCr [（DppNCH）_2]，4，这是由于Cr（iii）还原为Cr（ii）并保留了基于配体的自由基。醇盐配合物CpCr [（DppNCH）_2]（OCR _2R'）（5：R = Me，R'= Ph; 6：R = iPr，R'= H）通过Cp _2Cr与HOCR _2R'的质子分解合成。存在中性二亚胺和催化碱。相应的自由基吡啶-亚胺络合物CpCr（PyCHNMes）Cl（9），CpCr（PyCHNMes）（8）和CpCr（PyCHNMes）（OCMe _2Ph）（11）均通过类似方法制备。用碘氧化8可得到CpCr（PyCHNMes）I（10），其中在保留阴离子吡啶-亚胺自由基配体的情况下，再次发生Cr（ii）氧化为Cr（iii）。配合物1、2、4-8、10和11的分子结构通过单晶X射线衍射确定。在报道的配合物的紫外可见光谱中观察到不寻常的低能带，其中Cr（ii）配合物4和8观察到特别强的跃迁。通过理论计算研究了吡啶-亚胺配合物8和10的电子结构。

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