Abstract
The compounds [CyRu(η2-Ph2PCH(Me)Ph2PO)L][SbF6]2, where Cy = p-CH3C6H4CH(CH3)2; L = pyridine, 2; 3,5-lutidine, 3; isoquinoline, 4, were synthesized by chloride abstraction from [CyRu(η2-Ph2PCH(Me)Ph2PO)Cl][SbF6], 1, followed by treatment of the intermediate Lewis acid [CyRu(η2-Ph2PCH(Me)Ph2PO)][SbF6]2 with the appropriate ligand. Characterization by elemental analysis, 1H, 31P{1H}, VT NMR spectroscopy, and IR spectroscopy indicated that 2−4 were obtained as a mixture of exo and endo diastereomers (de = 14−60%). The endo diastereomer of compound 2 was also characterized by X-ray crystallography which revealed the (RRu*,RC*) relative configuration of the two stereogenic centers within the molecule. In contrast to analogues with other neutral donors, 31P{1H} NMR spectroscopy experiments demonstrated that 2−4 were stable to diastereomer interconversion in solution. This suggests that epimerization of the ruthenium center in an intermediate exo-[CyRu(η2-Ph2PCH(Me)Ph2PO)][SbF6]2 occurred by a path unavailable to 2−4 by inversion of the Ru(η2-Ph2PCH(Me)Ph2PO) ring.
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