Ethylene Rotation in Chiral Octahedral Rhenium(I) Complexes

A series of complexes of the type [TpRe(CO)(LD)(η2-ethylene)] has been synthesized, where LD is t BuNC, PMe3, pyridine, 1-methylimidazole, or NH3 (increasing in electron-donating ability of LD). The rates of the propeller-like rotation of ethylene about the ethylene−rhenium bond have been determined...

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Bibliographic Details
Published in:Organometallics 2001-04, Vol.20 (8), p.1699-1702
Main Authors: Friedman, Lee A, Meiere, Scott H, Brooks, Benjamin C, Harman, W. Dean
Format: Article
Language:English
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Summary:A series of complexes of the type [TpRe(CO)(LD)(η2-ethylene)] has been synthesized, where LD is t BuNC, PMe3, pyridine, 1-methylimidazole, or NH3 (increasing in electron-donating ability of LD). The rates of the propeller-like rotation of ethylene about the ethylene−rhenium bond have been determined using spin saturation transfer experiments at low temperatures (−85 to −60 °C). It was found that the ΔG ⧧ values correlate with both the C⋮O stretching frequencies and Re(II/I) reduction potentials for these complexes, indicating that the barrier to rotation is primarily electronic in nature.
ISSN:0276-7333
1520-6041
DOI:10.1021/om000865l