title: Platinum phosphinothiolato hydride complexes: synthesis, structure and evaluation as tin-free hydroformylation catalysts.
abstract: Ligand 2-diphenylphosphinothiophenol (Hsarp) reacted with Pt(PPh3)4 to yield trans-[PtH(sarp)(PPh3)], which undergoes fast exchange with free PPh3 on the NMR time scale and very slowly and reversibly formed some cis-[PtH(sarp)(PPh3)] over time in solution (11%, 24 h). Reaction of trans-[PtH(sarp)(PPh3)] with Hsarp in boiling toluene gave cis- and trans-[Pt(sarp)2]; the cis isomer being more stable. These complexes were characterized by (1)H and (31)P NMR and also analyzed by XRD in the case of trans-[PtH(sarp)(PPh3)], trans-[Pt(sarp)2], and cis-[Pt(sarp)2]. trans-[PtH(sarp)(PPh3)] was evaluated as a preformed, tin-free hydroformylation catalyst on styrene and found active at 100 °C, at pressures over 75 bar, yielding phenylpropanal (regioselectivities up to 83% in 2-phenylpropanal), with total conversions to aldehydes up to 100% at styrene/platinum ratios from 400/1 to 1000/1 and minimal hydrogenation products.
authors.affiliation: Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona, Spain. juli.real@uab.cat.
authors.forename: Julio
authors.initials: J
authors.lastname: Real
authors.affiliation: Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona, Spain. juli.real@uab.cat.
authors.forename: Esther
authors.initials: E
authors.lastname: Prat-Gil
authors.affiliation: Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona, Spain. juli.real@uab.cat.
authors.forename: Montserrat
authors.initials: M
authors.lastname: Pagès-Barenys
authors.affiliation: Departament de Química, Universitat de Girona. Campus de Montilivi, 17071 Girona, Spain.
authors.forename: Alfonso
authors.initials: A
authors.lastname: Polo
authors.affiliation: Servei de Difracció de Raigs-X, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona, Spain.
authors.forename: Joan F
authors.initials: JF
authors.lastname: Piniella
authors.affiliation: Servei de Difracció de Raigs-X, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona, Spain.
authors.forename: Ángel
authors.initials: Á
authors.lastname: Álvarez-Larena