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A pyrimidine thiolate Rh(I) complex: structure, bonding and one-dimensional interactions in solid and in solution.

Abstract

The reaction of [Rh(micro-Cl)(COD)]2 with 4,6-dimethyl-pyrimidinethiolate (Me2-pymt) and subsequent substitution of COD by CO yields [Rh(Me2-pymt)(CO)2]. The stacking pattern found in this compound is in contradiction with previously studied comparable square-planar complexes of type d8-[M(chelate)(monodentate)2] in which each ligand has different pi-acidic character. A theoretical study of the intermolecular interactions and conformation of the title compound has been carried out, combining semi-empirical band calculations on the real chains and ab initio(MP2 level) calculations on a model dimer. The combination of electronic and steric effects determines the rotation of the successive monomers and the deviation from linearity of the one-dimensional stacks. Its behaviour in solution is also special, developing a blue colour and forming micelles, when adding water to acetone solutions.

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Santiago Alvarez, Gabriel Aullón, Rosa Fandos, José Luis García Fierro, Pilar Ocón, Antonio Otero, Sergio Rojas, Pilar Terreros. 2005-02-03. A pyrimidine thiolate Rh(I) complex: structure, bonding and one-dimensional interactions in solid and in solution.. https://doi.org/10.1039/b416038j

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