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Issue 32, 2018
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Synthesis, electronic structure and redox properties of the diruthenium sandwich complexes [Cp*Ru(μ-C10H8)RuCp*]x (x = 0, 1+; Cp* = C5Me5; C10H8 = naphthalene)

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Abstract

The dinuclear ruthenium complex [Cp*Ru(μ-C10H8)RuCp*] (1; Cp* = η5-C5Me5) was prepared by reduction of the cationic precursor [Cp*Ru(η6-C10H8)]PF6 with KC8. Diamagnetic 1 has a symmetric molecular structure with an anti-facial configuration of the Cp*Ru moieties coordinating to naphthalene. Density Functional Theory (DFT) studies showed an electronic structure similar to that of the analogous diiron complex [Cp*Fe(μ-C10H8)FeCp*]. Cyclic voltammetry and UV-vis spectroelectrochemistry showed that 1 can be reversibly oxidized to 1+ and 12+. Chemical oxidation with [Cp2Fe]BArF4 afforded the paramagnetic compound [1]BArF4, which was investigated by EPR, single-crystal X-ray diffractometry and DFT calculations. Reaction of 1 with Brookhart's acid gave the hydride complex [3]BArF4, which was characterized spectroscopically and crystallographically. Cyclic voltammetry showed that [3]+ is converted back to 1 upon reduction and oxidation.

Graphical abstract: Synthesis, electronic structure and redox properties of the diruthenium sandwich complexes [Cp*Ru(μ-C10H8)RuCp*]x (x = 0, 1+; Cp* = C5Me5; C10H8 = naphthalene)

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Publication details

The article was received on 17 May 2018, accepted on 04 Jul 2018 and first published on 06 Jul 2018


Article type: Paper
DOI: 10.1039/C8DT02003E
Citation: Dalton Trans., 2018,47, 11058-11069
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    Synthesis, electronic structure and redox properties of the diruthenium sandwich complexes [Cp*Ru(μ-C10H8)RuCp*]x (x = 0, 1+; Cp* = C5Me5; C10H8 = naphthalene)

    D. Herrmann, C. Rödl, B. de Bruin, F. Hartl and R. Wolf, Dalton Trans., 2018, 47, 11058
    DOI: 10.1039/C8DT02003E

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