An Ru-Substituted Tris(ethynyl)methyl Cation: Synthesis, Properties, and Structure of [{Cp(dppe)Ru(C≡C)}3C]PF6·C6H6*
Michael I. Bruce
A C , Alexandre Burgun A , Brian K. Nicholson B and Natasha N. Zaitseva A
A Department of Chemistry, School of Physical Sciences, University of Adelaide, Adelaide, SA 5005, Australia.
B Department of Chemistry, University of Waikato, Hamilton 3216, New Zealand.
C Corresponding author. Email: michael.bruce@adelaide.edu.au
Australian Journal of Chemistry 73(6) 552-555 https://doi.org/10.1071/CH19655
Submitted: 18 December 2019 Accepted: 17 January 2020 Published: 5 March 2020
Abstract
The dark blue complex [{Cp(dppe)Ru(C≡C)}3C]PF6 1 (Cp = cyclopentadienyl, dppe = 1,2-bis(diphenylphosphino)ethane) was obtained in 46 % yield by treatment of Ru(C≡CH)(dppe)Cp with CuCl/TMEDA (tetramethylethanediamine), followed by KOH and [NH4]PF6 in acetone; it was accompanied by known complexes {Cp(dppe)Ru}C≡CC≡C{Ru(dppe)Cp} 2 (22 %) and yellow [1,3-{Cp(dppe)Ru}2C4H3]PF6 3 (2.6 %). The structure of the cationic fragment of 1 in its benzene solvate consists of a central planar C attached to three C≡CRu(dppe)Cp fragments. The cation of 3 consists of a cyclobuten-1,3-diyl group bearing two Ru(dppe)Cp groups. The 13C NMR resonance of the central C in 1 is found at δ 66.11. The cyclic voltammogram of 1 contains three irreversible oxidation waves at +0.87, +0.79, and +0.25 V, together with a reversible reduction wave at −1.38 V (versus FeCp2/[FeCp2]+).
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