Metal- and ligand-assisted CO2 insertion into Ru-C, Ru-N, and Ru-O bonds of ruthenium(II) phosphine complexes: a density functional theory study.
作者： Prabha Vadivelu , Cherumuttathu H. Suresh
DOI: 10.1021/IC5022577
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摘要: The CO2 insertion reactions of [L4Ru(η2-CH2C6H4)] (1), [L4Ru(η2-OC6H3Me)] (2), and [L4Ru(η2-NHC6H4)] (3), where L = PH3 PMe3, are modeled using density functional theory methods. In 1 2, the metal-assisted occurs because favorable initial axial phosphine dissociation mechanism, whereas in 3, ligand (NHC6H4)-assisted mechanism operates (ΔG⧧ +19.0 kcal/mol), wherein nucleophilic affinity −NHC6H4 moiety aids process. mechanisms consistent with experimental findings by Hartwig et al. (J. Am. Chem. Soc, 1991, 113, 6499), which rate 2 depends on added concentration, reaction 3 is independent concentration. preferably inserted into Ru–Caryl bond rather than competitive Ru–CH2 Ru–O bonds, respectively. 1, π-type orbital interaction aryl ring metal center found to stabilize tr...
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