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

journal contribution
posted on 2023-05-20, 08:02 authored by Rebecca FullerRebecca Fuller, Griffith, CS, Koutsantonis, GA, Skelton, BW, White, AH
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.

History

Publication title

Organometallics

Volume

34

Issue

11

Pagination

2632-2646

ISSN

0276-7333

Department/School

School of Natural Sciences

Publisher

Amer Chemical Soc

Place of publication

1155 16Th St, Nw, Washington, USA, Dc, 20036

Rights statement

© 2015 American Chemical Society

Repository Status

  • Restricted

Socio-economic Objectives

Expanding knowledge in the chemical sciences

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