The ability to convert simple hydrocarbons into higher value commodity chemicals catalytically is of great importance to the chemical industry. Aryl-gold complexes readily react with iridium, osmium and rhenium carbonyl complexes and alkyl-gold with osmium-carbonyl complexes to yield new organo-gold-iridium, organo-gold-osmium and organo-gold-rhenium bimetallic cluster compounds that can serve as models for hydrocarbon-transition metal interactions in heterogeneous catalysis. Reaction of Ru5(μ5-C)(CO)15, 1 with PhAu(NHC) yielded two new compounds: Ru5C(CO)14(Ph)[µ-Au(NHC)], 2 and Ru5C(CO)13(µ-η2-Ph)[Au(NHC)], 3 by oxidative addition of the Au – C bond to the Ru5 cluster. Compound 3 contains a µ - η – σ – π phenyl ligand that is dynamically interchanging its coordination between the two sides of the ring on the 1H NMR time scale at room temperature. Compounds 2 and 3 both react with CO to yield the CO insertion product Ru5C(CO)14(µ-η2-O=CPh)[Au(NHC)], 4. The reaction of Ru5(μ5-C)(CO)15, 1 and MeAu(PPh3) was also studied and yielded three new compounds: Ru5(μ5-C)(CO)14(μ-η2-O=CMe)[μ-Au(PPh3)], 5; Ru5(μ5-C)(CO)13(μ-η2-O=CMe)(Me)[μ-Au2(PPh3)2], 6 and Ru5(μ5-C)(CO)14(μ-η2-O=CMe)(η1-O=CMe)[μ-Au2(PPh3)2], 7 by the oxidative-additions of the the Au – C bond of one and two equivalents of the MeAu(PPh3) to the Ru5 cluster. The additions involve a cluster opening cleavage of one of the Ru – Ru bonds accompanied by the loss of one or more CO ligands. Bridging acetyl ligands were formed by facile CO insertion reactions. Compound 5 reacts with PPh3 to yield the PPh3 derivative Ru5(μ5-C)(CO)13(PPh3)(μ-η2-O=CMe)[μ-Au(PPh3)], 8. Compound 7 was obtained from 6 by the addition of CO with insertion into the Ru – CH3 bond at room temperature. Compound 6 eliminates acetone when heated under CO to yield the digold complex Ru5(μ5-C)(CO)11(μ-CO)3[μ-Au(PPh3)]2, 9 and small amounts of the new tetragold complex Ru5(μ5-C)(CO)11(μ-CO)2[μ-Au(PPh3)]4 10. Compound 9 also reacts with MeAu(PPh3) to yield 10. Recent studies with formyl groups have revealed similar chemistry that eliminates the need for the use of gold in some of these reactions. The transformations of the new acyl-ruthenium clusters will be presented as well.

Organometallic chemistry of ruthenium-gold carbonyl cluster complexes containing aryl and alkyl ligands

254th National Meeting (2017)

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