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- W1986486172 abstract "The indenyl effect has been introduced to pentadienyl (open cyclopentadienyl) chemistry by preparation of the phenylmethallyl (open indenyl) ligand oInd(Me). The reaction of its potassium salt K(oInd(Me)) with [(η(5)-C(5)Me(5))RuCl](4) afforded the sandwich complex [(η(5)-C(5)Me(5))Ru(η(5)-oInd(Me))] (1), which, upon treatment with PMe(3), CO, and 2,6-dimethylphenyl isocyanide (CN-o-Xy), easily underwent η(5)-η(3) hapticity interconversion and formed the complexes [(η(5)-C(5)Me(5))Ru(η(3)-oInd(Me))(L)] (2, L = PMe(3); 3, L = CO; 4, L = CN-o-Xy). In these complexes, the η(3)-bound phenylmethallyl ligand adopts an anti-conformation with regard to the relative positions of the phenyl and methyl substituents. For the PMe(3) complex anti-2, slow conversion to the syn-isomer was observed, and this equilibrium reaction was monitored by NMR spectroscopy at 50 °C to determine a first order rate constant of k(323 K) = 6.57 × 10(-6) (± 0.02 × 10(-6)) s(-1) and an activation barrier of ΔG° = 26.8 kcal mol(-1). DFT calculations afforded a stabilization of syn-2 and syn-3 by ΔG(298) = -1.54 and -1.74 kcal mol(-1) over the respective anti-isomer." @default.
- W1986486172 created "2016-06-24" @default.
- W1986486172 creator A5029172893 @default.
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- W1986486172 creator A5041488286 @default.
- W1986486172 creator A5049371244 @default.
- W1986486172 creator A5089476171 @default.
- W1986486172 date "2011-01-01" @default.
- W1986486172 modified "2023-10-18" @default.
- W1986486172 title "Facile η5–η3 hapticity interconversion in pentamethylcyclopentadienyl ruthenium(ii) complexes containing a phenylmethallyl (“open indenyl”) ligand" @default.
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- W1986486172 doi "https://doi.org/10.1039/c1dt11436k" @default.
- W1986486172 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/21952146" @default.
- W1986486172 hasPublicationYear "2011" @default.
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