Resumen: The number of late transition metal complexes bearing tridentate monoanionic silyl-based NSiN-type ligands has grown in the last few years. This review describes the synthetic methodologies that allow preparation of NSiN ligands precursors as well as the chemical and structural behavior of the transition metal complexes resulting from the reaction of these ligand precursors with different metallic starting materials. In addition, a description of the catalytic processes based on Rh- and Ir-NSiN catalysts so far reported is included. Moreover, an analysis of the chemistry of iridium complexes with different fac-K 3-(Si, N, N)-NSiN ligands allows to conclude that the nature of the silyl group along with the donor ability of the nitrogen atoms at the NSiN ligands influence on the reactivity and potential catalytic activity of the respective complexes. Idioma: Inglés DOI: 10.1016/j.ccr.2017.04.011 Año: 2017 Publicado en: COORDINATION CHEMISTRY REVIEWS 350 (2017), 49-60 ISSN: 0010-8545 Factor impacto JCR: 14.499 (2017) Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 1 / 45 = 0.022 (2017) - Q1 - T1 Factor impacto SCIMAGO: 4.342 - Chemistry (miscellaneous) (Q1)