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DOI: 10.1039/A905492H (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 3451-3462

Bis(acetylacetonato)bis(cyclooctene)ruthenium(II), cis-[Ru(acac)2(η2-C8H14)2]: a synthetic precursor to trans- and cis-bis(acetylacetonato)ruthenium(II) complexes[hair space]†

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Martin A. Bennett, Guandolina Chung, David C. R. Hockless, Horst Neumann and Anthony C. Willis

Abstract

Reduction of [Ru(acac)3] with zinc amalgam or zinc dust in hot THF containing some water in the presence of an excess of cyclooctene generated in solution cis-[Ru(acac)2(η2-C8H14)2], which cannot be isolated in solid form but has been identified on the basis of its 1H NMR spectrum. It is a useful synthetic precursor because the co-ordinated olefins are easily displaced by many ligands. Treatment with pyridine, tert-butyl isocyanide, tertiary phosphines, phosphites and triphenylarsine (L) at room temperature gave red-brown complexes trans-[Ru(acac)2L2], which isomerise in solution to the more stable cis compounds on heating. In contrast, the similarly prepared trimethylamine complex, trans-[Ru(acac)2(NMe3)2], does not undergo trans to cis isomerisation. Reaction of cis-[Ru(acac)2(η2-C8H14)2] with acetonitrile or triphenylstibine (L′) gave monosubstitution products cis-[Ru(acac)2(η2-C8H14)L′], which react on heating with an excess of L′ to give cis-[Ru(acac)2L′2]. Treatment of cis-[Ru(acac)2(η2-C8H14)2] (1 mol) with Ph2PCH2PPh2 (dppm) (2 mol) at room temperature gave trans-[Ru(acac)2(η1-dppm)2], whereas the ligands Ph2P(CH2)mPPh2 (L–L, m = 2, dppe; m = 3, dppp) under the same conditions gave oligomers [{Ru(acac)2(L–L)}n], which probably contain mutually trans-phosphorus atoms. On heating all three compounds are converted into cis-[Ru(acac)2(L–L)]. Treatment of trans-[Ru(acac)2L2] (L = NMe3 or PPh3) with CO at room temperature and pressure gave trans-[Ru(acac)2(CO)L], which, in the case of L = PPh3, isomerises to the cis compound on heating; reaction of trans-[Ru(acac)2(AsPh3)2] with CO under the same conditions gave cis-[Ru(acac)2(CO)(AsPh3)] directly. The structures of trans-[Ru(acac)2(CNBut)2], trans-[Ru(acac)2(PMePh2)2], cis-[Ru(acac)2(CNBut)2] (in the form of a molecular adduct with [Ru(acac)3]), cis-[Ru(acac)2(PMePh2)2] and trans-[Ru(acac)2(η1-dppm)2] have been determined by X-ray crystallography, and trends in the metal–ligand distances are discussed. The formation of trans-[Ru(acac)2L2] from cis-[Ru(acac)2(η2-C8H14)2] may proceed via a square-pyramidal intermediate [Ru(acac)2L].

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