Disulfido iron–manganese carbonyl cluster complexes: Synthesis, structure, bonding and properties of the radical CpFeMn2(CO)7(μ3-S2)2
详细信息 查看全文
- 作者：Richard D. Adams ; Erin M. Boswell ; Burjor Captain ; Shaobin Miao ; Chad Beddie ; Charles Edwin Webster ; Michael B. Hall ; Naresh S. Dalal ; Narpinder Kaur ; David Zipse
- 关键词：Manganese ; Iron ; Disulfido ; Radical ; Molecular orbitals
- 刊名：Journal of Organometallic Chemistry
- 出版年：2008
- 出版时间：1 August 2008
- 年：2008
- 卷：693
- 期：16
- 页码：2732-2738
- 全文大小：629 K
文摘
Two new compounds CpFeMn2(CO)7(μ3-S2)2 (2) and Cp3Fe3Mn(CO)4(μ3-S2)2(μ3-S) (3) were obtained by the treatment of [CpFeMn(CO)5(μ3-S2)]2 (1) with CO at room temperature in the presence of room light. Compound 2 contains two triply bridging disulfido ligands on opposite sides of an open FeMn2 triangular cluster. EPR and temperature-dependent magnetic susceptibility measurements show that it is paramagnetic with one unpaired electron per formula equivalent. The electronic structure of 2was established by DFT and Fenske-Hall (FH) molecular orbital calculations which show that the unpaired electron occupies a low lying antibonding orbital that is located principally on the iron atom. The cyclic voltammogram of 2 exhibits one reversible one-electron oxidation wave at +0.34 V and one irreversible one-electron reduction wave at −0.66 V vs. Ag/AgCl. Compound 3 contains three iron atoms and one manganese atom with two triply bridging disulfido ligands and one triply bridging sulfido ligand and has no unpaired electrons. The molecular structures of compounds 2 and 3 were established by single crystal X-ray diffraction analyses.