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

Abstract

© 2015 American Chemical Society. (Chemical Equation Presented) A number of group 11 salts, [MX] (M = Ag, X < sup > - < /sup > = < sup > - < /sup > O < inf > 3 < /inf > SCF < inf > 3 < /inf > , < sup > - < /sup > O < inf > 2 < /inf > CCF < inf > 3 < /inf > , BF < inf > 4 < /inf > < sup > - < /sup > ; M = Cu; X = Cl, Br) and [Cu(MeCN) < inf > 4 < /inf > ][PF < inf > 6 < /inf > ], were found to react in varying stoichiometries with ethyne-1,2-diyl compounds, [{Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} < inf > 2 < /inf > (µ < inf > 2 < /inf > -C=C)] (R = H, Me), to give a number of complex cations. The trication salts [Ag < inf > 3 < /inf > ({Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > Me)} < inf > 2 < /inf > (µ < inf > 2 < /inf > -? < sup > 1 < /sup > :? < sup > 1 < /sup > -C= C)) < inf > 3 < /inf > ](O < inf > 3 < /inf > SCF < inf > 3 < /inf > ) < inf > 3 < /inf > , [Ag < inf > 3 < /inf > ({Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} < inf > 2 < /inf > (µ < inf > 2 < /inf > -? < sup > 1 < /sup > :? < sup > 1 < /sup > -C=C))({Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} < inf > 2 < /inf > (µ < inf > 2 < /inf > -? < sup > 1 < /sup > :? < sup > 2 < /sup > -C= C)) < inf > 2 < /inf > ](BF < inf > 4 < /inf > ) < inf > 3 < /inf > , and [Cu < inf > 3 < /inf > ({Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} < inf > 2 < /inf > (µ < inf > 2 < /inf > -? < sup > 1 < /sup > :? < sup > 2 < /sup > -C=C))({Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} < inf > 2 < /inf > (µ < inf > 2 < /inf > -? < sup > 2 < /sup > -C=C))](PF < inf > 6 < /inf > ) < inf > 3 < /inf > result from the use of the respective anion salts in their syntheses. Coordination of Ag < sup > + < /sup > by the ethyne-1,2-diyl complexes in the presence of F < inf > 3 < /inf > CCO < inf > 2 < /inf > < sup > - < /sup > yields the tetranuclear complexes [Ag < inf > 4 < /inf > ({Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} < inf > 2 < /inf > (µ < inf > 2 < /inf > -? < sup > 2 < /sup > -C=C)) < inf > 2 < /inf > ](µ < inf > 2 < /inf > -O < inf > 2 < /inf > CCF < inf > 3 < /inf > ) < inf > 4 < /inf > (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 < inf > 2 < /inf > (µ-Cl) < inf > 2 < /inf > ({Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} < inf > 2 < /inf > (? < sup > 2 < /sup > -C= C))] < inf > (8|8) < /inf > , 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 < sup > + < /sup > /[{Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 5 < /inf > )} < inf > 2 < /inf > (µ < inf > 2 < /inf > -C=C)] have been probed spectroscopically, and the {Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} environments appear to be equivalent and, likewise, the resonances attributable to their C=C units. In a subsequent reaction of [{Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} < inf > 2 < /inf > (µ < inf > 2 < /inf > -C=C)] and AgBF < inf > 4 < /inf > use of a strict Ag < sup > + < /sup > /ethyne-1,2-diyl ratio gave [Ag({Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 5 < /inf > )} < inf > 2 < /inf > (? < sup > 2 < /sup > -C=C)) < inf > 2 < /inf > ](BF < inf > 4 < /inf > ). The analogous Cu < sup > + < /sup > adduct [Cu({Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 5 < /inf > )} < inf > 2 < /inf > (? < sup > 2 < /sup > -C= C)) < inf > 2 < /inf > ](PF < inf > 6 < /inf > ) is observed, along with the tricopper(I) adduct from the reaction of [{Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} < inf > 2 < /inf > (µ < inf > 2 < /inf > -C=C)] and [Cu(NCMe) < inf > 4 < /inf > ](PF < inf > 6 < /inf > ). 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.