[Re2Cp2(CO) 6+]2+的阳极制剂:一个二度式二分法,提供强大的单电子氧化剂[ReCp2(CO) 3+]
Daesung Chong1, Ayman Nafady, Paulo Jorge Costa
1Department of Chemistry, University of Vermont, Burlington, Vermont 05405, USA.
Journal of the American Chemical Society
|November 10, 2005
概括
半三明治钢琴便化合物被氧化成持久的17电子Re (II) 电离子. 这些离子通过Re-Re键形成稳定的二次离子,使其能够被分离并用作强氧化剂.
科学领域:
- 有机金属化学 有机金属化学
- 电化学 电化学 电化学
- 计算化学计算化学
背景情况:
- 半三明治钢琴子化合物,特别是Re (((η5-C5R5) (((CO) 3 (1, R = H; 2, R = Me),在有机金属化学中很重要.
- 了解氧化金属复合物的电化学行为和稳定性对于开发新的合成方法至关重要.
研究的目的:
- 用电化学方法氧化半三明治钢琴便化合物到它们相应的17电子Re (II) 电离子.
- 研究这些基离子在溶液和固态中的稳定性和反应性.
- 探索这些氧化物种作为强单电子氧化剂的潜力.
主要方法:
- 在CH2Cl2/[Bu4N][B(C6F5) 4中的玻璃碳电极上对化合物的阳极氧化.
- 电化学测量,包括循环电压测量,以确定还原电位 (E1⁄2).
- 密度函数理论 (DFT) 计算以阐明氧化物种中的电子结构和结合.
- 制备性阳极电化学,用于分离纯盐.
主要成果:
- Re ((η5-C5R5) ((CO) 3化合物被成功氧化为持久的17电子Re ((II) 电离子,具有高正氧化还原潜力.
- 基离子与二次离子处于平衡状态,通过金属-联体轨道重杂化形成的长 Re-Re 键 (≈3.3 Å) 稳定.
- 纯盐, [1][B(C6F5)4]2和 [2][B(C6F5)4]2被分离出来,证明了氧化形式的稳定性.
- 孤立的盐 [1][B(C6F5)4]2 作为一种稳定的储存形式,用于强大的单电子氧化剂 [1]+.
结论:
- 半三明治钢琴子复合物的单电子氧化产生持久的17电子Re (II) 电离子.
- 通过Re-Re键的二元化是这些高度氧化物种的关键稳定机制.
- 准备电化学为分离和利用这些强大的单电子氧化剂在合成中提供了一条可行的途径.
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