Synthesis of the cyclohexadienyl ruthenium arene complexes [(η5-C6H3Me4)Ru(η6-arene)]+ from the dimethyloctadienyl ruthenium chloride[(μ-η3:η3-C10H16)RuCl2]2

Add time:09/26/2019    Source:sciencedirect.com

Reaction of the readily accessible dimethyloctadienyl ruthenium chloride [(μ-η3:η3-C10H16)RuCl2]2 (1) with 1,3,5,5-tetramethylcyclohexadiene and arenes in the presence of TlPF6 gives cyclohexadienyl ruthenium arene complexes [(η5-C6H3Me4)Ru(η6-arene)]+ in ca. 50% yield (arene = benzene, naphthalene, pyrene, thiophene, ethyl ester of N-acetyl-phenylalanine). In the absence of appropriate arene the major product is the mesitylene complex [(η5-C6H3Me4)Ru(η6-C6H3Me3)]+ formed via splitting of the C–Me bond in the 1,3,5,5-tetramethylcyclohexadienyl ligand. The reaction of 1 with p-xylene and TlPF6 in the absence of diene gives a methyl-isobutyl substituted pentadienyl complex [(η5-C5H5(iBu)Me)Ru(η6-C6H4Me2)]+ (6) via isomerization of the dimethyloctadienyl ligand. The structures of [(η5-C6H3Me4)Ru(η6-naphthalene)]PF6 and [6]BPh4 were confirmed by X-ray diffraction.

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