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

作者：Fuller Rebecca O; Griffith Christopher S; Koutsantonis George A^*; Skelton Brian W; White Allan H

来源：Organometallics, 2015, 34(11): 2632-2646.

DOI：10.1021/om501270u

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)(eta-C5H4R)}2(mu(2)-C equivalent to C)] (R = H, Me), to give a number of complex cations. The trication salts [Ag-3({Ru(CO)(2)(eta-C5H4Me)}(2)(mu(2)-eta(1):eta(1)-C equivalent to C))(3)](O3SCF3)(3), [Ag-3({Ru(CO)(2)(eta-C5H4R)}(2)(mu(2)-eta(1):eta(1)-C equivalent to C))({Ru(CO)(2)(eta-C5H4R)}(2)(mu(2)-eta(1):eta(2)-C equivalent to C))(2)](BF4)(3), and [Cu-3({Ru(CO)(2)(eta-C5H4R)}(2)(mu(2)-eta(1):eta(2)-C equivalent to C))({Ru(CO)(2)(eta-C5H4R)}(2)(mu(2)-eta(2)-C equivalent to 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 F(3)CCO2 yields the tetranuclear complexes [Ag-4({Ru(CO)(2)(eta-C5H4R)}(2)(mu(2)-eta(2)-C equivalent to C))(2)](mu(2)-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 [Cu-2(mu-Cl)(2)({Ru(CO)(2)(mu-C5H4R)}(2)(eta(2)-C equivalent to C))]((infinity|infinity)), 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)(eta-C5H5)}(2)(mu(2)-C equivalent to C)] have been probed spectroscopically, and the {Ru(CO)(2)(eta-C5H4R)} environments appear to be equivalent and, likewise, the resonances attributable to their C=C units. In a subsequent reaction of [{Ru(CO)(2)(eta-C5H4R)}(2)(mu(2)-C equivalent to C)] and AgBF4 use of a strict Ag+/ethyne-1,2-diyl ratio gave [Ag({Ru(CO)(2)(eta-C5H5)}(2)(mu(2)-C equivalent to C))(2)](BF4). The analogous Cu+ adduct [Cu({Ru(CO)(2)(eta-C5H5)}(2)(mu(2)-C equivalent to C))(2)](PF6) is observed, along with the tricopper(I) adduct from the reaction of [{Ru(CO)(2)(eta-C5H4R)}(2)(mu(2)-C equivalent to 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.

• 出版日期2015-6-8