title: A Ligand-Free Pt3Cluster Catalyzes the Markovnikov Hydrosilylation of Alkynes with up to 106Turnover Frequencies.
abstract: The Pt-catalyzed hydrosilylation of alkynes is the procedure of choice to obtain vinylsilanes, and is claimed to be the most relevant application of Pt in organic synthesis. More than half a century after its discovery, only β-vinylsilanes (anti-Markovnikov addition) are obtained with simple Pt catalysts, whereas α-vinylsilanes (Markovnikov addition) remain elusive compounds. Here the catalysis of the Markovnikov hydrosilylation of terminal alkynes by Pt3clusters, in parts-per-million amounts, to give a wide variety of α-vinylsilanes in reasonable isolated yields and with turnover frequencies that can reach up to one million per hour is reported. Moreover, these α-vinylsilanes are reactive in well-stablished C-C bond-forming cascade reactions, in which the corresponding β-isomers are unreactive. Besides its efficiency and synthetic usefulness, this catalytic system is an excellent example of how the atom-by-atom aggregation of a catalytic metal leads to a different selectivity for a given reaction.
authors.affiliation: Instituto de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas, Avda. de los Naranjos s/n, 46022, Valencia, Spain.
authors.forename: Miguel A
authors.identifier: http://orcid.org/0000-0002-3860-0947
authors.initials: MA
authors.lastname: Rivero-Crespo
authors.affiliation: Instituto de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas, Avda. de los Naranjos s/n, 46022, Valencia, Spain.
authors.forename: Antonio
authors.identifier: http://orcid.org/0000-0003-1063-5811
authors.initials: A
authors.lastname: Leyva-Pérez
authors.affiliation: Instituto de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas, Avda. de los Naranjos s/n, 46022, Valencia, Spain.
authors.forename: Avelino
authors.identifier: http://orcid.org/0000-0002-2232-3527
authors.initials: A
authors.lastname: Corma
keywords: alkynes; cluster compounds; hydrosilylation; platinum; silanes