Characterization of the low-energy electronic excited states of benzoyl-substituted ruthenocenes.
Characterization of the low-energy electronic excited states of benzoyl-substituted ruthenocenes.
复制标题
苯甲酰取代的钌茂的低能电子激发态的表征。
DOI：
10.1021/ic0482178
复制
发表时间：
2005
影响因子：
4.6
通讯作者：
Kutal,Charles
中科院分区：
文献类型：
--
作者：
Sanderson,CynthiaT;Quinlan,JessicaA;Conover,RichardC;Johnson,MichaelK;Murphy,Michael;Dluhy,RichardA;Kutal,Charles
Electronic absorption and resonance Raman spectral studies of benzoylruthenocene (BRc) and 1,1‘-dibenzoylruthenocene (DRc) indicate that the low-energy electronic excited states of these 4d6metallocenes possess metal-to-ligand charge transfer (MLCT) character. While this MLCT contribution should weaken the metal-ring bonding in the excited state, neither compound is photosensitive in nonhalogenated solvents such as methanol, acetonitrile, and cyclohexane. In contrast, irradiating BRc and DRc in the good electron-accepting solvent, carbon tetrachloride, results in ring loss via a pathway that appears to originate from a charge-transfer-to-solvent excited state. Both metallocenes function as photoinitiators for the anionic polymerization of ethyl 2-cyanoacrylate, and the kinetics and mechanism of this process have been investigated. Comparing the present results on BRc and DRc with those reported earlier for the corresponding benzoyl-substituted ferrocene compounds reveals some interesting commonalities and differences between the excited-state properties of these 3d and 4d metallocenes.
