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Influence of cyclopentadienyl ring-tilt on electron-transfer reactions: Redox-induced reactivity of strained 2 and 3 Ruthenocenophanes

Influence of cyclopentadienyl ring-tilt on electron-transfer reactions: Redox-induced reactivity of strained 2 and 3 Ruthenocenophanes

Russell, Andrew D., Gilroy, Joe B., Lam, Kevin ORCID: 0000-0003-1481-9212, Haddow, Mairi F., Harvey, Jeremy N., Geiger, William E. and Manners, Ian (2014) Influence of cyclopentadienyl ring-tilt on electron-transfer reactions: Redox-induced reactivity of strained 2 and 3 Ruthenocenophanes. Chemistry - A European Journal, 20 (49). pp. 16216-16227. ISSN 0947-6539 (Print), 1521-3765 (Online) (doi:https://doi.org/10.1002/chem.201403512)

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Abstract

In contrast to ruthenocene Ru((5)-C5H5)(2) and dimethylruthenocene Ru((5)-C5H4Me)(2) (7), chemical oxidation of highly strained, ring-tilted 2ruthenocenophane Ru((5)-C5H4)(2)(CH2)(2) (5) and slightly strained 3ruthenocenophane Ru((5)-C5H4)(2)(CH2)(3) (6) with cationic oxidants containing the non-coordinating B(C6F5)(4)(-) anion was found to afford stable and isolable metalmetal bonded dicationic dimer salts Ru((5)-C5H4)(2)(CH2)(2)(2)B(C6F5)(4)(2) (8) and Ru((5)-C5H4)(2)(CH2)(3)(2)B(C6F5)(4)(2) (17), respectively. Cyclic voltammetry and DFT studies indicated that the oxidation potential, propensity for dimerization, and strength of the resulting RuRu bond is strongly dependent on the degree of tilt present in 5 and 6 and thereby degree of exposure of the Ru center. Cleavage of the RuRu bond in 8 was achieved through reaction with the radical source (CH3)(2)NC(S)SSC(S)N(CH3)(2) (thiram), affording unusual dimer (CH3)(2)NCS2Ru((5)-C5H4)((3)-C5H4)C2H4(2)B(C6F5)(4)(2) (9) through a haptotropic (5)-(3) ring-slippage followed by an apparent 2+2 cyclodimerization of the cyclopentadienyl ligand. Analogs of possible intermediates in the reaction pathway C6H5ERu((5)-C5H4)(2)C2H4B(C6F5)(4) E=S (15) or Se (16) were synthesized through reaction of 8 with C6H5EEC6H5 (E=S or Se).

Item Type: Article
Uncontrolled Keywords: Electron-transfer reactions, Organometallic chemistry, Ruthenium
Subjects: Q Science > QC Physics
Q Science > QD Chemistry
Faculty / Department / Research Group: Faculty of Engineering & Science
Faculty of Engineering & Science > Department of Pharmaceutical, Chemical & Environmental Sciences
Last Modified: 10 Oct 2017 16:07
Selected for GREAT 2016: None
Selected for GREAT 2017: None
Selected for GREAT 2018: None
Selected for GREAT 2019: None
URI: http://gala.gre.ac.uk/id/eprint/17719

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