Probing hydrogen bond networks in half-sandwich Ru(II) building blocks by a combined 1H DQ CRAMPS solid-state NMR, XRPD, and DFT approach

Michele R Chierotti; Roberto Gobetto; Carlo Nervi; Alessia Bacchi; Paolo Pelagatti; Valentina Colombo; Angelo Sironi

doi:10.1021/ic401762z

Probing hydrogen bond networks in half-sandwich Ru(II) building blocks by a combined 1H DQ CRAMPS solid-state NMR, XRPD, and DFT approach

Inorg Chem. 2014 Jan 6;53(1):139-46. doi: 10.1021/ic401762z. Epub 2013 Dec 16.

Authors

Michele R Chierotti¹, Roberto Gobetto, Carlo Nervi, Alessia Bacchi, Paolo Pelagatti, Valentina Colombo, Angelo Sironi

Affiliation

¹ Department of Chemistry and NIS Centre of Excellence, University of Torino , Via P. Giuria 7, 10125 Torino, Italy.

PMID: 24341446
DOI: 10.1021/ic401762z

Abstract

The hydrogen bond network of three polymorphs (1α, 1β, and 1γ) and one solvate form (1·H2O) arising from the hydration-dehydration process of the Ru(II) complex [(p-cymene)Ru(κN-INA)Cl2] (where INA is isonicotinic acid), has been ascertained by means of one-dimensional (1D) and two-dimensional (2D) double quantum (1)H CRAMPS (Combined Rotation and Multiple Pulses Sequences) and (13)C CPMAS solid-state NMR experiments. The resolution improvement provided by homonuclear decoupling pulse sequences, with respect to fast MAS experiments, has been highlighted. The solid-state structure of 1γ has been fully characterized by combining X-ray powder diffraction (XRPD), solid-state NMR, and periodic plane-wave first-principles calculations. None of the forms show the expected supramolecular cyclic dimerization of the carboxylic functions of INA, because of the presence of Cl atoms as strong hydrogen bond (HB) acceptors. The hydration-dehydration process of the complex has been discussed in terms of structure and HB rearrangements.