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Issue 6, 2019
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O–H and (CO)N–H bond weakening by coordination to Fe(ii)

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Abstract

New N,N′-dimethyl-N,N′-bis(2-pyridylmethyl)-ethane-1,2-diamine derivatives bearing covalently linked OH and (CO)NH groups have been synthesized. The coordination of those pendant hydroxyl/amide groups to a Fe(II) metal center is demonstrated both in solution, even in the presence of chloride as the counterion, and in solid state, by means of X-ray diffraction crystal structures. As a result of this coordination, the experimental bond dissociation free energies (BDFE) of O–H and (CO)N–H bonds are remarkably diminished down to 76.0 and 80.5 kcal mol−1 respectively, which is also in agreement with DFT-based theoretical calculations. These BDFE values are in the range of commonly used hydrogen-atom donor reagents. The strategy presented here allows an unequivocal evaluation of the influence of metal coordination in X–H bond weakening in organic solvents which could be easily extended to other metal centers.

Graphical abstract: O–H and (CO)N–H bond weakening by coordination to Fe(ii)

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Article information


Submitted
27 Nov 2018
Accepted
10 Jan 2019
First published
11 Jan 2019

Dalton Trans., 2019,48, 2179-2189
Article type
Paper

O–H and (CO)N–H bond weakening by coordination to Fe(II)

S. Resa, A. Millán, N. Fuentes, L. Crovetto, M. Luisa Marcos, L. Lezama, D. Choquesillo-Lazarte, V. Blanco, A. G. Campaña, D. J. Cárdenas and J. M. Cuerva, Dalton Trans., 2019, 48, 2179
DOI: 10.1039/C8DT04689A

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