170224 20260407115449.0 doi 10.3389/fchem.2026.1804159 sideral 148714 ART-2026-148714 eng Batuecas, María Universidad de Zaragoza (orcid)0000-0002-1430-1440 Transition metal complexes with asymmetric tridentate peripheral organosilyl ligands: their impact in homogeneous catalysis 2026 Silyl-based tridentate ligands [SiL2]n− (n = 1, 2; L = PR3, NR2 or other groups) have emerged over the last decades as a versatile class of ligands for transition metal (TM) chemistry. TM–(κ3-Si,L2) complexes display unique structural features and reactivity that arise directly from the incorporation of a strongly σ-donating silyl group into the pincer ligand framework. While most studies have focused on systems where silicon occupies the central position of the tridentate scaffold, recent efforts have shifted toward the development of TM complexes in which the silicon atom is located at the periphery of the ligand. This alternative design opens unexplored opportunities to fine-tune electronic and steric properties, offering fresh perspectives for catalyst optimization and the discovery of unprecedented reactivity patterns. This review summarizes and discusses the most recent advances in this emerging area, highlighting strategies for incorporating peripheral silicon into the skeleton of the ligand and exploring its impact on the coordination chemistry, reactivity and catalytic activity of the resulting TM complexes. Access copy available to the general public Unrestricted info:eu-repo/grantAgreement/ES/DGA/E42-23R info:eu-repo/semantics/openAccess by https://creativecommons.org/licenses/by/4.0/deed.es info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Oro, Luis A. Universidad de Zaragoza (orcid)0000-0001-7154-7239 Fernández-Álvarez, Francisco J. Universidad de Zaragoza (orcid)0000-0002-0497-1969 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 14 (2026), 1804159 [12 pp.] Front. chem. Frontiers in Chemistry 2296-2646 4303971 http://zaguan.unizar.es/record/170224/files/texto_completo.pdf Versión publicada 2349355 http://zaguan.unizar.es/record/170224/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:170224 articulos driver 2026-03-26-14:32:03 ARTICLE