A novel terphenylphosphine PMe2Ar(Dipp2) () (Dipp = 2,6-(i)Pr2C6H3) forms stable Pt(0) complexes with ethene and 3,3-dimethylbut-1-ene that behave as sources of the reactive Pt(PMe2Ar(Dipp2)) fragment. The complexes are efficient catalysts for the selective hydrosilylation of terminal alkynes.
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http://dx.doi.org/10.1039/c5cc07308a | DOI Listing |
Nat Commun
November 2024
Instituto de Investigaciones Químicas (IIQ), Departamento de Química Inorgánica and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Sevilla and Consejo Superior de Investigaciones Científicas (CSIC), Sevilla, Spain.
Pairing transition metals and heavier tetrylenes (Si, Ge, Sn, Pb) holds great potential for cooperative bond activation and catalysis. In this work, we investigate the reactivity of a low-coordinate Pt(0)/Ge(II) system that emerges from the reaction between the monoligated platinum(0) precursor [(PMeAr)Pt(olefin)] with germylene dimer [ArGeCl] (where Ar = CH-2,6-(CH-2,6-Pr)). The resulting complex reveals ability for cooperative bond activation.
View Article and Find Full Text PDFJ Am Chem Soc
October 2021
School of Chemical Sciences, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, Illinois61801, United States.
We describe the synthesis, characterization, and catalytic hydrosilylation activity of platinum(II) di-ω-alkenyl compounds of stoichiometry PtR, where R = CHSiMe(vinyl) () or CHSiMe(allyl) (), and their adducts with 1,5-cyclooctadiene (COD), dibenzo[,]cyclooctatetraene (DBCOT), and norbornadiene (NBD), which can be considered as slow-release sources of the reactive compounds and . At loadings of 0.5 × 10-5 × 10 mol %, is an active hydrosilylation catalyst that exhibits heat-triggered latency: no hydrosilylation activity occurs toward many olefin substrates even after several hours at 20 °C, but turnover numbers as high as 200000 are seen after 4 h at 50 °C, with excellent selectivity for formation of the anti-Markovnikov product.
View Article and Find Full Text PDFDalton Trans
February 2018
Adam Mickiewicz University in Poznań, Faculty of Chemistry, Umultowska 89b, 61-614 Poznań, Poland.
Platinum complexes bearing bulky N-heterocyclic carbene (NHC) ligands, i.e., [Pt(IPr*)(dvtms)] (where, IPr* = 1,3-bis{2,6-bis(diphenylmethyl)-4-methylphenyl}imidazol-2-ylidene) and [Pt(IPr*OMe)(dvtms)] (where, IPr*OMe = 1,3-bis{2,6-bis(diphenylmethyl)-4-methoxyphenyl}imidazol-2-ylidene, dvtms = divinyltetramethyldisiloxane) catalyse nearly quantitatively and highly or completely the selective hydrosilylation of terminal olefins as well as terminal or internal acetylenes.
View Article and Find Full Text PDFDalton Trans
July 2017
Science & Technology, Dow Corning Toray, Ichihara, Chiba 299-0108, Japan.
A platinum(0) complex bearing a cyclic (alkyl)(amino)silylene and a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (DVTMS) was synthesized and isolated in the form of colorless crystals. The single-crystal X-ray diffraction analysis of this complex in combination with theoretical calculations indicated that the Pt→Si π-back-donation in this complex is weaker than that in the corresponding cyclic-dialkylsilylene-ligated Pt complex. The performance of this complex in the catalytic hydrosilylation of (MeSiO)MeSi-H with various terminal alkenes that contain functional groups was comparable to that of the corresponding cyclic dialkylsilylene/DVTMS Pt(0) complex.
View Article and Find Full Text PDFChem Commun (Camb)
December 2015
Instituto de Investigaciones Químicas (IIQ), Departamento de Química Inorgánica and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Sevilla and Consejo Superior de Investigaciones Científicas (CSIC), Avenida Américo Vespucio, 49, 41092 Sevilla, Spain.
A novel terphenylphosphine PMe2Ar(Dipp2) () (Dipp = 2,6-(i)Pr2C6H3) forms stable Pt(0) complexes with ethene and 3,3-dimethylbut-1-ene that behave as sources of the reactive Pt(PMe2Ar(Dipp2)) fragment. The complexes are efficient catalysts for the selective hydrosilylation of terminal alkynes.
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