Electrochemistry of Octamethyl[3]ruthenocenophane: Synthesis and Structure of the First Dicationic Derivative of Ruthenocene, [{η55-C5Me4(CH2)3C5Me4}Ru(NCMe)](PF6)2

Kiyonari Hashidzume, Hiromi Tobita, Hiroshi Ogino

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Abstract

The octamethyl[3]ruthenocenophane {η55-C5Me4(CH2)3C5Me4}Ru (1) was synthesized by the reaction of RuCl3·3H2O with HC5Me4(CH2)3C5Me4H in triethylene glycol at 200 °C. Other sterically congested ruthenocene derivatives, (η5-C5Me5)2Ru (2) and (η5-C5Me4H)2Ru (3), were also prepared in high yields by this simple method. The cyclic voltammogram of 1 in CH2Cl2 shows a reversible 1e oxidation wave at E1/2 = +0.36 V vs SCE, while that in CH3CN exhibits a 2e oxidation wave at +0.30 V vs SCE and a smaller 2e reduction wave at —0.04 V vs SCE. The bulk electrolysis of 1 at +0.30 V vs SCE in 0.1 M NH4PF6/CH3CN gave the dication salt containing CH3CN as an additional ligand, [{η55-C5Me4(CH2)3C5Me4}Ru(NCMe)](PF6)2(4), almost quantitatively. The ECE mechanism including the CH3CN coordination/dissociation process was suggested for the redox reaction between 1 and its dication [1·NCCH3]2+ based on the cyclic voltammograms of 1–4 as well as the crystal structure analysis of 1 and 4. Crystal data for 1: C21H30Ru, space group P21/a, a = 15.272(2) Å, b = 11.090(1) Å, c = 10.991(2)Å, β = 101.07(2)°, V = 1826.8(4) Å3, Z = 4, R = 0.052, and Rw= 0.084 based on 4435 reflections with [|Fo| > 3σ(Fo)]. Crystal data for 4: C23H33F12NP2Ru, space group Pmnm, a = 11.031(1) Å, b = 14.883(1) Å, c = 8.973(1) Å, V = 1473.1(2) Å3, Z = 2, R = 0.059, and Rw= 0.085 based on 2528 reflections with [|Fo| > 3σ(Fo)].

Original languageEnglish
Pages (from-to)1187-1194
Number of pages8
JournalOrganometallics
Volume14
Issue number3
DOIs
Publication statusPublished - 1995 Mar

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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