Abstract
Novel, functionalized, chiral Cp-ligands with S- and P-donor atoms were designed. Together with known analogues containing ether side-chains they were complexed to ruthenium for use as chiral Lewis-acid catalysts. In the ether complexes [RuCl(η5-C5H4CH2CH2OR)(PPh3)2] {R = Me, (1S)-isobornyl, (1R)-menthyl, (1R)-fenchyl} the Cp-ligand is only η5-coordinated; all attempts to provoke a bidentate, Cp/O coordination were unsuccessful. The sulfide complex [Ru{η5:η1-C5H4CH2CH2S[(1R)-neomenthyl]}(PPh3)2][OTf] contains a bidentate Cp/S-coordinated ligand, but it is unstable. The stable phosphane complex [RuCl(η5:η1-C5H4CH2CH(Me)PPh2)(PPh3)] exists as a 77:23 mixture of diastereomers containing a strongly bidentate Cp/P ligand. The diastereomers interchange, with Ru–Cl bond cleavage as the rate-determining step.
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