Anion-Directed Solid-State Structures of Copper(I) and Silver(I) Adducts of Ruthenium Ethyne-1,2-diyl Compounds

Becky Fuller, Christopher Griffith, George Koutsantonis, Brian Skelton, Allan White

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

© 2015 American Chemical Society. (Chemical Equation Presented) A number of group 11 salts, [MX] (M = Ag, X- = -O3SCF3, -O2CCF3, BF4-; M = Cu; X = Cl, Br) and [Cu(MeCN)4][PF6], were found to react in varying stoichiometries with ethyne-1,2-diyl compounds, [{Ru(CO)2(η-C5H4R)}2(μ2-C≡C)] (R = H, Me), to give a number of complex cations. The trication salts [Ag3({Ru(CO)2(η-C5H4Me)}2(μ2-η11-C≡ C))3](O3SCF3)3, [Ag3({Ru(CO)2(η-C5H4R)}2(μ2-η11-C≡C))({Ru(CO)2(η-C5H4R)}2(μ2-η12-C≡ C))2](BF4)3, and [Cu3({Ru(CO)2(η-C5H4R)}2(μ2-η12-C≡C))({Ru(CO)2(η-C5H4R)}2(μ2-η2-C≡C))](PF6)3 result from the use of the respective anion salts in their syntheses. Coordination of Ag+ by the ethyne-1,2-diyl complexes in the presence of F3CCO2- yields the tetranuclear complexes [Ag4({Ru(CO)2(η-C5H4R)}2(μ2-η2-C≡C))2](μ2-O2CCF3)4 (R = H, Me). The reaction of CuCl does not afford the discrete dimeric complexes normally observed for internal alkynes and metal alkynyl complexes but, rather, the 1-D polymer [Cu2(μ-Cl)2({Ru(CO)2(η-C5H4R)}2(η2-C≡ C))](∞|∞), while CuBr gives the discrete dimer motif known in the literature. The solution structures at 1/2, 1/1, and 2/1 stoichiometries of Ag+/[{Ru(CO)2(η-C5H5)}2(μ2-C≡C)] have been probed spectroscopically, and the {Ru(CO)2(η-C5H4R)} environments appear to be equivalent and, likewise, the resonances attributable to their C≡C units. In a subsequent reaction of [{Ru(CO)2(η-C5H4R)}2(μ2-C≡C)] and AgBF4 use of a strict Ag+/ethyne-1,2-diyl ratio gave [Ag({Ru(CO)2(η-C5H5)}2(η2-C≡C))2](BF4). The analogous Cu+ adduct [Cu({Ru(CO)2(η-C5H5)}2(η2-C≡ C))2](PF6) is observed, along with the tricopper(I) adduct from the reaction of [{Ru(CO)2(η-C5H4R)}2(μ2-C≡C)] and [Cu(NCMe)4](PF6). A combination of factors appears to control the solid-state structures of these coinage metal adducts, with the anion found to be that which influences the packing to the greatest extent.
Original languageEnglish
Pages (from-to)2632-2646
JournalOrganometallics
Volume34
Issue number11
Early online date29 May 2015
DOIs
Publication statusPublished - 8 Jun 2015

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