Rasmus Stichauer, Arne Helmers, J. Bremer
Feb 7, 2017
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Influential Citations
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Organometallics
Abstract
We describe rhenium(I) triscarbonyl compounds (3 and 4) decorated with simple-to-use 2-iminomethyl-pyridine (1, impy) and 2-aminomethyl-pyridine (2, ampy) ligands, respectively, which can serve as cooperative ligand scaffolds enabling CO2 binding via a formal [1,3] addition under Re–O and C–C bond formation. fac-[Re(impy)(CO)3Br] (3) is readily prepared by stirring (1-(pyridin-2-yl)-N-(p-tolyl)methanimine (impy, 1) and [Re(CO)5Br] in refluxing THF. Alternatively, complex 3 can be readily obtained when a mixture of [Re(CO)5Br], p-toluidine, and picolinaldehyde is refluxed in ethanol. Complex 3 is reduced with excess potassium metal in THF (two-electron reduction) to give the anionic amido complex K[Re(amidopy*)(CO)3] (5b, the asterisk indicates the dearomatized ligand). Analysis of the 1H and 13C{1H} NMR spectra of 5b suggest the dearomatization of the pyridine unit. Complex 5b is highly reactive and gives rise to the facile [1,3] addition of CO2. The addition of the CO2 and thus the formation of K[Re(amid...