Granted Patent
B2
US 12,551,876 · App. 17/921,012 · Granted Feb 17, 2026
Coordinated platinum hydrosilylation catalysts with COOH based ligands
Inventors:
Steven L. Tait, Jr. (Bloomington, IN); Iyad Syed Ali (Chesterton, IN); Linxiao Chen (Issaquah, WA)
Assignee:
THE TRUSTEES OF INDIANA UNIVERSITY
B01J31/2239B01J23/10B01J31/1815B01J31/26C07F7/1876B01J2231/323B01J2235/00B01J2235/10B01J2235/30B01J2531/828
View Patent ↗
Loading inventors, assignments & file history…
Abstract
The invention describes metal catalysts such as Pt single-site centers on metal oxide supports, e.g., powdered supports, such as MgO, Al 2 O 3 , CeO 2 or mixtures thereof with phenyl or biphenyl ligands substituted with two or more carboxylic acid groups.
Claims (24)
1 . A supported platinum catalyst system comprising: (a) an anchoring ligand comprising a multi-carboxylic acid phenyl or biphenyl ligand, (b) a platinum metal ion, (c) a support and (d) 3,6-di-2-pyridyl-1,2,4,5-tetrazine (DPTZ).
2 . The supported platinum catalyst system of claim 1 , wherein the anchoring ligand multi-carboxylic acid phenyl or biphenyl ligand has at least two carboxylic acid groups.
3 . The supported platinum catalyst system of claim 2 , wherein the at least two carboxylic acid groups are positioned meta or para to each other about the phenyl or biphenyl ring.
4 . The supported platinum catalyst of claim 1 , wherein the anchoring ligand multi-carboxylic acid phenyl or biphenyl ligand comprises one of the formulae:
or mixtures thereof.
5 . The supported platinum catalyst system of claim 1 , wherein the support comprises MgO, Al 2 O 3 , CeO 2 or mixtures thereof.
6 . A process comprising:
(a) providing a supported catalyst system of claim 5 ;
(b) contacting the supported catalyst system, a vinyl terminated alkene and a hydrosilylation agent under hydrosilylation conditions; and
(c) hydrosilylating the vinyl terminated alkene to form a hydrosilylated alkyl product.
7 . The process of claim 6 , wherein the vinyl terminated alkene is 1-octene.
8 . The process of claim 6 , wherein the hydrosilylation agent comprises dimethoxymethylsilane.
9 . The supported platinum catalyst of claim 1 , wherein the multi-carboxylic acid phenyl or biphenyl ligand comprises one of the formulae:
10 . The supported platinum catalyst system of claim 9 , wherein the support comprises MgO.
11 . The supported platinum catalyst system of claim 9 , wherein the support comprises Al 2 O 3 .
12 . The supported platinum catalyst system of claim 9 , wherein the support comprises CeO 2 .
13 . The supported platinum catalyst system of claim 9 , wherein the support comprises one or more of MgO, Al 2 O 3 , or CeO 2 .
14 . The supported platinum catalyst of claim 1 , wherein the multi-carboxylic acid phenyl or biphenyl ligand comprises
15 . The supported platinum catalyst of claim 1 , wherein the multi-carboxylic acid phenyl or biphenyl ligand comprises:
16 . The supported platinum catalyst of claim 1 , wherein the multi-carboxylic acid phenyl or biphenyl ligand comprises:
17 . The supported platinum catalyst of claim 1 , wherein the multi-carboxylic acid phenyl or biphenyl ligand comprises a mixture of:
18 . The supported platinum catalyst system of claim 1 , wherein the support comprises MgO.
19 . The supported platinum catalyst system of claim 1 , wherein the support comprises Al 2 O 3 .
20 . The supported platinum catalyst system of claim 1 , wherein the support comprises CeO 2 .
Assignments (2)
CONFIRMATORY LICENSE
Recorded May 30, 2023
From: INDIANA UNIVERSITY
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 063803/0115 →
ASSIGNMENT OF ASSIGNOR'S INTEREST
Recorded Oct 25, 2022
From: TAIT, STEVEN L., JR.; CHEN, LINXIAO; ALI, IYAD SYED
To: THE TRUSTEES OF INDIANA UNIVERSITY
Reel/Frame 061527/0850 →
Continuity (2)
Provisional Application
63017977
· Apr 30, 2020
References Cited (90)
US 3775452A
· Karstedt
· 1973
[cited by applicant]
US 20090247397A1
· Mashima
· 2009
[cited by examiner]
WO WO2007099449A2
· 2007
[cited by examiner]
L. Chen et al., 365 Journal of Catalysis, 303-312 (2018) (Year: 2018).
[cited by examiner]
Chen et al., 365 Journal of Catalysis, 303-312 (2018) (Year: 2018).
[cited by examiner]
D. Kunwar et al., 9 ACS Catalysis, 3978-3990 (2019) (Year: 2019).
[cited by examiner]
Z. Zhang et al., 10 Nature Communications, 1-7 (2019) (Year: 2019).
[cited by examiner]
G. Vilé et al., 54 Angew. Chem. Int. Ed., 11265-11269, (2015) (Year: 2015).
[cited by examiner]
D. Skomski et al., 134 Journal of the American Chemical Society, 9862-9864 (2014) (Year: 2014).
[cited by examiner]
L. Chen et al., 11 ChemCatChem, 2843-2854 (2019) (Year: 2019).
[cited by examiner]
PCT International Search Report and Written Opinion completed by the ISA/US on Jun. 21, 2021 and issued in connection with PCT/US2021/029782.
[cited by applicant]
(Chen, Let al.) Alkene Hydrosilylation on Oxide-Supported Pt-Ligand Single-Site Catalysts. ChemCatChem. Jun. 2019, Epub Apr. 25, 2019, vol. 11, No. 12; pp. 2843-2854.
[cited by applicant]
Sommer, L., et al., Peroxide-catalyzed addition of trichlorosilane to 1-octene. J. Am. Chem. Soc. 1947, 69, 188-188.
[cited by applicant]
Pierce, O.R., et al., Fluorosilicones as high temperature elastomers. J. Elastoplastics, vol. 3, (Apr. 1971), p. 82-96.
[cited by applicant]
Marciniec, B., et al., Organosilicon Chemistry V-From Molecules to Materials. Wiley VCH, Weinheim 2003.—Book Reference.
[cited by applicant]
Morita, Y., et al., Thermally initiated cationic polymerization and properties of epoxy siloxane. J. Appl. Polym. Sci. 2006, 100, 2010-2019.
[cited by applicant]
Beyou, E., et al., New fluorinated polysiloxanes containing an ester function in the spacer. I. Synthesis and characterization. J. Polym. Sci., Part A: Polym. Chem. 1994, 32, 1673-1681.
[cited by applicant]
Iojoiu, C., et al., Synthesis and photocrosslinking of benzyl acrylate substituted polydimethylsiloxanes. Eur. Polym. J. 2000, 36, 2115-2123.
[cited by applicant]
Li, Z., et al., Synthesis and structural characterization of a new polysiloxane with second-order nonlinear optical effect. J. Appl. Polym. Sci. 2004, 94, 769-774.
[cited by applicant]
Sellinger, A., et al., Palladium-and platinum-catalyzed coupling reactions of allyloxy aromatics with hydridosilanes and hydridosiloxanes: Novel liquid crystalline/organosilane materials. J. Polym. Sci., Part A: Polym. …
[cited by applicant]
Drazkowski, D.B., et al., Chemical substituent effects on morphological transitions in styrene-butadiene-styrene triblock copolymer grafted with polyhedral oligomeric silsesquioxanes. Macromolecules 2006, 39, 1854-1863.
[cited by applicant]
Tuchbreiter, A., et al., “A posteriori” modification of carbosilane dendrimers and dendrons: their activation in core and branch positions. Dalton Trans. 2005, 1394-1402.
[cited by applicant]
Troegel, D., et al., Recent advances and actual challenges in late transition metal catalyzed hydrosilylation of olefins from an industrial point of view. Coord. Chem. Rev. 2011, 255, 1440-1459.
[cited by applicant]
Jerschow, P., Silicone elastomers; Smart Publications, 2001; vol. 137.—Book Reference.
[cited by applicant]
Morris, R. H., Asymmetric hydrogenation, transfer hydrogenation and hydrosilylation of ketones catalyzed by iron complexes. Chem. Soc. Rev. 2009, 38, 2282-2291.
[cited by applicant]
Langlotz, B. K., et al., Chiral bis (pyridylimino) isoindoles: A highly modular class of pincer ligands for enantioselective catalysis. Angew. Chem. Int. Ed. 2008, 47, 4670-4674. In Angew. Chem. 2008, 120, 4748-4752.
[cited by applicant]
Bart, S. C., et al., Preparation and molecular and electronic structures of iron (0) dinitrogen and silane complexes and their application to catalytic hydrogenation and hydrosilation. J. Am. Chem. Soc. 2004, 126, 13794…
[cited by applicant]
Vankelecom, I., et al., Dense organic catalytic membranes for fine chemical synthesis. Catal. Today 2000, 56, 147-157. QD501 .C35 v.55-56 2000 B-ALF BTAA Print Archive (requested Oct. 31 1:13).
[cited by applicant]
Xue, M., et al., Effect of triarylphosphane ligands on the rhodium-catalyzed hydrosilylation of alkene. Appl. Organomet. Chem. 2014, 28, 120-126.
[cited by applicant]
Igarashi, M., et al., Ir-catalyzed hydrosilylation reaction of allyl acetate with octakis (dimethylsiloxy) octasilsesquioxane and related hydrosilanes. J. Organomet. Chem. 2014, 752, 141-146.
[cited by applicant]
Dong, H., et al., Rhenium-mediated dehydrogenative silylation and highly regioselective hydrosilylation of nitrile substituted olefins. J. Organomet. Chem. 2014, 750, 17-22.
[cited by applicant]
Wu, J. Y., et al., A strategy for the synthesis of well-defined iron catalysts and application to regioselective diene hydrosilylation. J. Am. Chem. Soc. 2010, 132, 13214-13216.
[cited by applicant]
Glaser, P.B., et al., Catalytic hydrosilylation of alkenes by a ruthenium silylene complex. Evidence for a new hydrosilylation mechanism. J. Am. Chem. Soc. 2003, 125, 13640-13641.
[cited by applicant]
Nozakura, S., et al., Cyanoethylation of Trichlorosilane. II. α-Addition. Bull. Chem. Soc. Jpn. 1956, 29, 326-331.
[cited by applicant]
Bareille, L., et al., First Titanium-Catalyzed a nti-1, 4-Hydrosilylation of Dienes. Organometallics 2005, 24, 5802-5806.
[cited by applicant]
Harder, S., et al., Rational Design of a Well-Defined Soluble Calcium Hydride Complex. Angew. Chem. Int. Ed. 2006, 45, 3474-3478.
[cited by applicant]
Speier, J.L., et al., The addition of silicon hydrides to olefinic double bonds. Part II. The use of group VIII metal catalysts. J. Am. Chem. Soc. 1957, 79, 974-979.
[cited by applicant]
Galeandro-Diamant, T., et al., Platinum nanoparticles in suspension are as efficient as Karstedt's complex for alkene hydrosilylation. Chem. Commun. 2015, 51, 16194-16196.
[cited by applicant]
Chauhan, B.P., et al., Regioselective Synthesis of Multifunctional Hybrid Polysiloxanes Achieved by Pt-Nanocluster Catalysis. J. Am. Chem. Soc. 2005, 127, 5790-5791.
[cited by applicant]
Bai, Y., et al., Use of functionalized PEG with 4-aminobenzoic acid stabilized platinum nanoparticles as an efficient catalyst for the hydrosilylation of alkenes. J. Colloid Interface Sci. 2013, 394, 428-433.
[cited by applicant]
Stein, J., et al., In situ determination of the active catalyst in hydrosilylation reactions using highly reactive Pt (0) catalyst precursors. J. Am. Chem. Soc. 1999, 121, 3693-3703.
[cited by applicant]
Meister, T.K., et al., Platinum Catalysis Revisited—Unraveling Principles of Catalytic Olefin Hydrosilylation. ACS Catal. 2016, 6, 1274-1284.
[cited by applicant]
Markó, I. E., et al., Selective and efficient platinum (0)-carbene complexes as hydrosilylation catalysts. Science 2002, 298, 204-206.
[cited by applicant]
Markó, I. E., et al., Highly Active and Selective Platinum(0)-Carbene Complexes. Efficient, Catalytic Hydrosilylation of Functionalised Olefins. Adv. Synth. Catal. 2004, 346, 1429-1434.
[cited by applicant]
Bernhammer, J. C., et al., Platinum (II) complexes with thioether-functionalized benzimidazolin-2-ylidene ligands: Synthesis, structural characterization, and application in hydroelementation reactions. Organometallics …
[cited by applicant]
Dunsford, J.J., et al., Expanded ring N-heterocyclic carbene complexes of zero valent platinum dvtms (divinyltetramethyldisiloxane): Highly efficient hydrosilylation catalysts. J. Organomet. Chem. 2011, 696, 188-194.
[cited by applicant]
Taige, M.A., et al., Platinum (II)-bis-(N-heterocyclic carbene) complexes: synthesis, structure and catalytic activity in the hydrosilylation of alkenes. J. Organomet. Chem. 2011, 696, 2918-2927.
[cited by applicant]
Sabourault, N., et al., Platinum oxide (PtO2): a potent hydrosilylation catalyst. Org. Lett. 2002, 4, 2117-2119.
[cited by applicant]
Chen, Y.J., et al., Discovering Partially Charged Single-Atom Pt for Enhanced Anti-Markovnikov Alkene Hydrosilylation. J. Am. Chem. Soc. 2018, 140, 7407-7410.
[cited by applicant]
Zhu, Y., et al., One-Pot Pyrolysis to N-Doped Graphene with High-Density Pt Single Atomic Sites as Heterogeneous Catalyst for Alkene Hydrosilylation. ACS Catal. 2018, 8, 10004-10011.
[cited by applicant]
Cui, X., et al., Synthesis of Single Atom Based Heterogeneous Platinum Catalysts: High Selectivity and Activity for Hydrosilylation Reactions. ACS Central Science 2017, 3, 580-585.
[cited by applicant]
Huang, Z., et al., Catalytically Active Single-Atom Sites Fabricated from Silver Particles. Angew. Chem. 2012, 124, 4274-4279.
[cited by applicant]
Fako, E.; Lodziana, Z.; Lopez, N., Comparative single atom heterogeneous catalysts (SAHCs) on different platforms: a theoretical approach. Catal. Sci. Technol. 2017, 7, 4285-4293.
[cited by applicant]
Chen, Y.X., et al., Fabrication, characterization, and stability of supported single-atom catalysts. Catalysis Science & Technology 2017, 7, 4250-4258.
[cited by applicant]
Vilé, G., et al., A Stable Single-Site Palladium Catalyst for Hydrogenations. Angew. Chem. Int. Ed. 2015, 54, 11265-11269.
[cited by applicant]
Xu, W., et al., Single-site SBA-15 supported zirconium catalysts. Synthesis, characterization and toward cyanosilylation reaction Single-site SBA-15 supported zirconium catalysts. Synthesis, characterization and toward …
[cited by applicant]
Ji, P., et al., Single-Site Cobalt Catalysts at New Zr8 (μ2-0)8 (μ2-OH)4 Metal-Organic Framework Nodes for Highly Active Hydrogenation of Alkenes, Imines, Carbonyls, and Heterocycles. J. Am. Chem. Soc. 2016, 138, 12234-…
[cited by applicant]
Schweitzer, N.M., et al., Propylene Hydrogenation and Propane Dehydrogenation by a Single-Site Zn2+ on Silica Catalyst. ACS Catal. 2014, 4, 1091-1098.
[cited by applicant]
Sohn, H., et al., Isolated, well-defined organovanadium (III) on silica: single-site catalyst for hydrogenation of alkenes and alkynes. Chem. Commun. 2017.
[cited by applicant]
Skomski, D., et al., Two- and Three-Electron Oxidation of Single-Site Vanadium Centers at Surfaces by Ligand Design. J. Am. Chem. Soc. 2015, 137, 7898-7902.
[cited by applicant]
Skomski, D., et al., Redox-active on-surface polymerization of single-site divalent cations from pure metals by a ketone-functionalized phenanthroline. J. Chem. Phys. 2015, 142, 101913.
[cited by applicant]
Skomski, D., et al., Redox-Active On-Surface Assembly of Metal-Organic Chains with Single-Site Pt(II). J. Am. Chem. Soc. 2014, 136, 9862-9865.
[cited by applicant]
Tempas, C.D., et al., Redox Isomeric Surface Structures Are Preferred over Odd-Electron Pt1+. Chem. Eur. J. 2018, 24, 15852-15858.
[cited by applicant]
Williams, C.G., et al., Metal-Ligand Complexation through Redox Assembly at Surfaces Characterized by Vibrational Spectroscopy. J. Phys. Chem. C 2017.
[cited by applicant]
Morris, T.W., et al., Multi-electron Reduction Capacity and Multiple Binding Pockets in Metal-Organic Redox Assembly at Surfaces. Chem. Eur. J. 2019, 25, 5565-5573.
[cited by applicant]
Chen, L., et al., Synthesis of platinum single-site centers through metal-ligand self-assembly on powdered metal oxide supports. J. Catal. 2018, 365, 303-312.
[cited by applicant]
Chen, L., et al., Alkene Hydrosilylation on Oxide-Supported Pt-Ligand Single-Site Catalysts. ChemCatChem 2019, 11, 2843-2854.
[cited by applicant]
Chen, L., et al., Sulfate promotion of selective catalytic reduction of nitric oxide by ammonia on ceria. Catalysis Science & Technology 2019, 9, 1802-1815.
[cited by applicant]
Iimura, T., et al., A Dialkylsilylene-Pt(0) Complex with a DVTMS Ligand for the Catalytic Hydrosilylation of Functional Olefins, Organometallics, 35 (2016) 4071-4076.
[cited by applicant]
Chen, L., et al., Bidentate N-based Ligands for Highly Reusable, Ligand-coordinated, Supported Pt Hydrosilylation Catalysts, ChemCatChem, 12 (2020) 3576-3584. Accepted Article, DOI: 10.1002/cctc.202000085.
[cited by applicant]
Tait, S.L., et al., Metal-Organic Coordination Interactions in Fe-Terephthalic Acid Networks on Cu(100), J. Am. Chem. Soc., 130 (2008) 2108-2113.
[cited by applicant]
Skomski, D., et al., Robust Surface Nano-Architecture by Alkali-Carboxylate lonic Bonding, Journal of the American Chemical Society, 134 (2012) 14165-14171.
[cited by applicant]
Ozer, D., et al., Synthesis and Characterization of Boric Acid Mediated Metal-organic Frameworks Based on Trimesic Acid and Terephthalic Acid, Journal of Molecular Structure, 1141 (2017) 261-267.
[cited by applicant]
Stepanow, S., et al., Deprotonation-Driven Phase Transformations in Terephthalic Acid Self-Assembly on Cu(100), J. Phys. Chem. B, 108 (2004) 19392-19397.
[cited by applicant]
Burns, F., et al., X-ray photoelectron spectroscopy of cadmium arachidate monolayers on various metal surfaces, J. Phys. Chem., 86 (1982) 5123-5127.
[cited by applicant]
Russat, J., Characterization of polyamic acid/polyimide films in the nanometric thickness range from spin-deposited polyamic acid, Surf. Interface Anal., 11 (1988) 414-420.
[cited by applicant]
Troughton, E.B., et al., Monolayer films prepared by the spontaneous self-assembly of symmetrical and unsymmetrical dialkyl sulfides from solution onto gold substrates: structure, properties, and reactivity of constitue…
[cited by applicant]
Taguchi, M., et al., Supercritical hydrothermal synthesis of hydrophilic polymer-modified water-dispersible CeO2 nanoparticles, CrystEngComm, 13 (2011) 2841-2848.
[cited by applicant]
Cheng, G., et al., Preparation of P(St-co-MAA)/CeO2 composite microspheres via surface carboxyl oxidation followed by in situ chemical deposition of CeO2 and their catalytic application on oxidative degradation of methy…
[cited by applicant]
Taguchi, M., et al., Growth Mechanism and Surface Chemical Characteristics of Dicarboxylic Acid-Modified CeO2 Nanocrystals Produced in Supercritical Water: Tailor-Made Water-Soluble CeO2 Nanocrystals, Cryst. Growth Des.…
[cited by applicant]
Schmidt, J.J., et al., Surface studies of polymer blends. 2. An ESCA and IR study of poly (methyl methacrylate)/poly (vinyl chloride) homopolymer blends, Macromolecules, 22 (1989) 4489-4495.
[cited by applicant]
Onishi, H., et al., Adsorption of Na atoms and oxygen-containing molecules on MgO(100) and (111) surfaces, Surf. Sci., 191 (1987) 479-491.
[cited by applicant]
Kallury, K.M.R., et al., Covalent binding of amino, carboxy, and nitro-substituted aminopropyltriethoxysilanes to oxidized silicon surfaces and their interaction with octadecanamine and octadecanoic acid studied by X-ra…
[cited by applicant]
Pakharukova, V.P.,, et al., Alumina-supported platinum catalysts: Local atomic structure and catalytic activity for complete methane oxidation, Appl. Catal. A, 486 (2014) 12-18.
[cited by applicant]
Beck, I.E., et al., Platinum nanoparticles on Al2O3: Correlation between the particle size and activity in total methane oxidation, J. Catal., 268 (2009) 60-67.
[cited by applicant]
Leich, V., et al., Hydrosilylation catalysis by an earth alkaline metal silyl; synthesis, characterization, and reactivity of pis (triphenylsilyl) calcium, Chem. Commun. 2014, 50, 2311-2314.
[cited by applicant]