om501270u_si_002.cif (4.48 MB)

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

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posted on 08.06.2015, 00:00 by Rebecca O. Fuller, Christopher S. Griffith, George A. Koutsantonis, Brian W. Skelton, Allan H. White
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)}22-CC)] (R = H, Me), to give a number of complex cations. The trication salts [Ag3({Ru­(CO)2(η-C5H4Me)}2211-CC))3]­(O3SCF3)3, [Ag3({Ru­(CO)2(η-C5H4R)}2211-CC))­({Ru­(CO)2(η-C5H4R)}2212-CC))2]­(BF4)3, and [Cu3({Ru­(CO)2(η-C5H4R)}2212-CC))­({Ru­(CO)2(η-C5H4R)}222-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)}222-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)}22-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)}22-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)}22-CC)] and AgBF4 use of a strict Ag+/ethyne-1,2-diyl ratio gave [Ag­({Ru­(CO)2(η-C5H5)}22-CC))2]­(BF4). The analogous Cu+ adduct [Cu­({Ru­(CO)2(η-C5H5)}22-CC))2]­(PF6) is observed, along with the tricopper­(I) adduct from the reaction of [{Ru­(CO)2(η-C5H4R)}22-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.