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• W2040382852 abstract "An analysis has been made of deviations from ideal centrosymmetric bonding of alkenes to transition metals in square-planar complexes. Three separate approaches have been employed. Firstly, the geometries obtained for a series of X-ray crystal structures of monosubstituted rhodium-alkene complexes have been obtained. Secondly, DFT computations on closely related rhodium-alkene complexes are reported. Thirdly. the data have been augmented by recourse to the crystal structure serach and retrieval file (CSSR) database to retrieve the X-ray data for square-planar ethene and monosubstituted alkene complexes. The results obtained from these analyses provide a consistent picture. Two distortions from ideality are important: twisting of the alkene about the axis between the metal (M) and the alkene centroid and rolling of the alkene around a cylinder enclosing the metal, such that the two C-M bonds remain equal in length. The presence of both of these is verified through both X-ray structure determinations and DFT calculations. For the rolling distortion, there is a relationship between the electronic character of the substituent on the alkene and the direction of roll. The net effect of this is to place the more nucleophilic carbon of the alkene closer to the square plane. The significance of this for the regiochemistry of the Heck reaction is briefly discussed." @default.
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• W2040382852 date "2000-12-15" @default.
• W2040382852 modified "2023-10-16" @default.
• W2040382852 title "The Chatt-Dewar-Duncanson Model Revisited: X-ray, DFT and NMR Studies of Rhodium-Alkene Binding—Deviations from Structural Ideality" @default.
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• W2040382852 doi "https://doi.org/10.1002/1521-3765(20001215)6:24<4587::aid-chem4587>3.0.co;2-6" @default.
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