4.5 Review

Arene-ruthenium(II) and osmium(II) complexes as catalysts for nitrile hydration and aldoxime rearrangement reactions

Journal

INORGANICA CHIMICA ACTA
Volume 517, Issue -, Pages -

Publisher

ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2020.120180

Keywords

Ruthenium; Osmium; Half-sandwich complexes; Homogeneous catalysis; Hydration of nitriles; Rearrangement of aldoximes

Funding

  1. Spanish Ministry of Economy, Industry and Competitiveness (MINECO) [CTQ2016-75986-P]
  2. University of Oviedo [PAPI-18-GR-2011-0032]
  3. MECD of Spain

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This short review provides a survey on the atom-economical routes for generating primary amides through catalytic hydration of nitriles and rearrangement of aldoximes, focusing on the extensively studied (?6-arene)-ruthenium(II) derivatives. Additionally, examples of (?6-arene)-osmium(II) complexes with comparable or superior effectiveness in hydrating nitriles have also been mentioned.
The catalytic hydration of nitriles and the rearrangement of aldoximes are atom-economical routes to generate primary amides of great academic and industrial interest. Among the different families of catalysts that have been developed for these transformations, the most extensively studied is that of (?6-arene)-ruthenium(II) derivatives since, by appropriate selection of the auxiliary ligands, high activities and selectivities can be reached under remarkably mild conditions. Very recently, some examples of (?6-arene)-osmium(II) complexes able to hydrate nitriles with effectiveness comparable or even superior to that of their ruthenium analogues have also appeared. In this short review a survey of this chemistry is presented.

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