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• W2972604810 abstract "Abstract The metathesis reaction of IrCl(CO)(PPh3)2 (4) and Vaska-type derivatives IrCl(CO)(PR3)2 (PR3 = MePh2, 5; Me2Ph, 6; Me3, 7) with 1–2 equivalents of the potassium butadienesulfinate salts K(SO2CHCRCHCH2) (R = H, 2; Me, 3) led to the formation of mixtures of chiral diastereomers “a” and “b” of general formula Ir(1–2,5-η-CH2CHCRCHSO2)(CO)(L)2 (R = H, L = PPh3, 8a,b; PMePh2, 9a,b; PMe2Ph, 10a,b; PMe3, 11a,b; R = Me, L = PPh3, 12a,b; PMePh2, 13a,b; PMe2Ph, 14a,b; PMe3, 15a,b) In isomer “a” both phosphine ligands L are located at the open mouth of the butadienesulfonyl ligand, and between the non-coordinated double bond of the same non-planar ligand, respectively; while the CO is opposite to the SO2 group. In isomer “b”, one phosphine remains in the open mouth of the butadienesulfonyl ligand, and the CO and the second phosphine have exchanged positions, being now the CO near to the SO2 group, and the phosphine opposite to the SO2 group. The most abundant isomer is assignable to a for 9a-11a and 12a-15a, while the opposite is observed in 8a and 12a with the bulkier triphenylphosphine. Electronic and predominant steric factors have been implicated as being most responsible for leading to a preference for one isomeric form over the other. A comparative study of these derivatives was carried out through the analysis of the IR, mass spectrometry, and 1H, 13C{1H} and 31P{1H} NMR, as well as through crystalline structures of 9a′, 11a, 12b′, 13a′, 14a and 15a, as well as precursors 5–7. The presence of the butadienesulfonyl ligand in all isomers 8a,b-15a,b induces a total asymmetry that is reflected through the 1H and 13C{1H} NMR, in addition to the preferred coordination mode (1–2,5-η-) of this ligand. Monitoring reactions through 1H and 31P{1H} NMR of 8a,b in CDCl3 and 9a,b in C6D6 and CDCl3 showed the influence of the temperature and solvent in the equilibrium of isomers in the reaction mixture." @default.
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• W2972604810 date "2019-11-01" @default.
• W2972604810 modified "2023-09-26" @default.
• W2972604810 title "Butadienesulfonyl iridium complexes with phosphine and carbonyl ligands" @default.
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• W2972604810 doi "https://doi.org/10.1016/j.jorganchem.2019.120929" @default.
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