CHEN LINXIAO (US)
WO2018107169A1 | 2018-06-14 |
US8471018B2 | 2013-06-25 |
GOOSSEN LUKAS J, RODRIGUEZ N., LINDER C., ZIMMERMANN B., LANGE P.: "Cu-Catalyzed Protodecarboxylation of Aromatic Carboxylic Acids", THE JOURNAL OF ORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY, vol. 74, no. 6, 1 January 2007 (2007-01-01), pages 1 - 1, XP055869517, ISSN: 0022-3263
ABEL ANTON S., YU MITROFANOV ALEXANDER, YAKUSHEV ALEKSEI A., ZENKOV ILYA S., MOROZKOV GLEB V., AVERIN ALEXEI D., BELETSKAYA IRINA : "1,10‐Phenanthroline Carboxylic Acids for Preparation of Functionalized Metal‐Organic Frameworks", ASIAN JOURNAL OF ORGANIC CHEMISTRY , 1(2), 160-165 CODEN: AJOCC7; ISSN: 2193-5807, WILEY - V C H VERLAG GMBH & CO. KGAA, GERMANY, vol. 8, no. 11, 1 November 2019 (2019-11-01), Germany , pages 2128 - 2142, XP055869520, ISSN: 2193-5807, DOI: 10.1002/ajoc.201900569
ABEL ANTON S., YU MITROFANOV ALEXANDER, YAKUSHEV ALEKSEI A., ZENKOV ILYA S., MOROZKOV GLEB V., AVERIN ALEXEI D., BELETSKAYA IRINA : "1,10‐Phenanthroline Carboxylic Acids for Preparation of Functionalized Metal‐Organic Frameworks", ASIAN JOURNAL OF ORGANIC CHEMISTRY , 1(2), 160-165 CODEN: AJOCC7; ISSN: 2193-5807, WILEY - V C H VERLAG GMBH & CO. KGAA, GERMANY, vol. 8, no. 11, 1 November 2019 (2019-11-01), Germany , pages 2128 - 2142, XP055869520, ISSN: 2193-5807, DOI: 10.1002/ajoc.201900569
HEWAT TRACY, MCDONALD SHANE, LEE JONATHAN, RAHMAN MAHFUJUR, CAMERON PETRA, HU FA-CHUN, CHI YUN, YELLOWLEES LESLEY J., ROBERTSON NE: "Varying numbers and positions of carboxylate groups on Ru dyes for dye-sensitized solar cells: uptake on TiO 2 , cell performance and cell stability", RSC ADV., vol. 4, no. 20, 7 February 2014 (2014-02-07), pages 10165 - 10175, XP055869549, DOI: 10.1039/C3RA47795A
HARA K, ET AL.: "NEW RU(II) PHENANTHROLINE COMPLEX PHOTOSENSITIZERS HAVING DIFFERENT NUMBER OF CARBOXYL GROUPS FOR DYE-SENSITIZED SOLAR CELLS", JOURNAL OF PHOTOCHEMISTRY, ELSEVIER, AMSTERDAM, NL, vol. 145, no. 01/02, 1 January 2001 (2001-01-01), AMSTERDAM, NL, pages 117 - 122, XP001172442, ISSN: 1010-6030, DOI: 10.1016/S1010-6030(01)00570-6
CALOGERO GIUSEPPE, BARTOLOTTA ANTONINO, DI MARCO GAETANO, DI CARLO ALDO, BONACCORSO FRANCESCO: "Vegetable-based dye-sensitized solar cells", CHEMICAL SOCIETY REVIEWS, ROYAL SOCIETY OF CHEMISTRY, UK, vol. 44, no. 10, 9 April 2015 (2015-04-09), UK , pages 3244 - 3294, XP055869550, ISSN: 0306-0012, DOI: 10.1039/C4CS00309H
WANG KAIXUAN, ZHAO WEILIANG, ZHANG QINGXIAO, LI HEXING, ZHANG FANG: "In Situ One-Step Synthesis of Platinum Nanoparticles Supported on Metal–Organic Frameworks as an Effective and Stable Catalyst for Selective Hydrogenation of 5-Hydroxymethylfurfural", ACS OMEGA, ACS PUBLICATIONS, US, vol. 5, no. 26, 25 June 2020 (2020-06-25), US , pages 16183 - 16188, XP055869553, ISSN: 2470-1343, DOI: 10.1021/acsomega.0c01759
WANG KAIXUAN, ZHAO WEILIANG, ZHANG QINGXIAO, LI HEXING, ZHANG FANG: "In Situ One-Step Synthesis of Platinum Nanoparticles Supported on Metal–Organic Frameworks as an Effective and Stable Catalyst for Selective Hydrogenation of 5-Hydroxymethylfurfural", ACS OMEGA, ACS PUBLICATIONS, US, vol. 5, no. 26, 25 June 2020 (2020-06-25), US , pages 16183 - 16188, XP055869553, ISSN: 2470-1343, DOI: 10.1021/acsomega.0c01759
CHEN LINXIAO; STERBINSKY GEORGE E.; TAIT STEVEN L.: "Synthesis of platinum single-site centers through metal-ligand self-assembly on powdered metal oxide supports", JOURNAL OF CATALYSIS, ACADEMIC PRESS, DULUTH, MN., US, vol. 365, 21 July 2018 (2018-07-21), US , pages 303 - 312, XP085441725, ISSN: 0021-9517, DOI: 10.1016/j.jcat.2018.07.004
WHAT IS CLAIMED IS: 1. A supported platinum catalyst system comprising: (a) a di-nitrogen ligand to complex with (b) a platinum metal ion, (c) a support and, optionally, (d) an anchoring ligand, wherein the di-nitrogen ligand comprises the formula: wherein R1 and R2 are each, independently, a C3 to a C12 branched or unbranched alkyl group, a substituted or unsubstituted phenyl group or a carboxylic acid group; wherein the optional anchoring ligand comprises 2,2′-bipyridine-4,4′- dicarboxylic acid or 1,10-phenanthroline-5,6-dione; and the biphenyl rings can form a third ring to form a phenanthroline ring system. 2. The supported platinum catalyst system of claim 1, wherein R1 and R2 are both an unbranched C9 alkyl group. 3. The supported platinum catalyst system of claim 1, wherein R1 and R2 are both an unsubstituted phenyl group. 4. The supported platinum catalyst system of claim 1, wherein R1 and R2 are both carboxylic acid. 5. The supported platinum catalyst system of claim 1, wherein the support comprises MgO, 6. The supported platinum catalyst system of claim 1, wherein the support comprises Al2O3. 7. The supported platinum catalyst system of claim 1, wherein the support comprises CeO2. 8. The supported platinum catalyst system of claim 1, wherein the support comprises MgO, Al2O3, CeO2 or mixtures thereof. 9. A process comprising: (a) providing a supported catalyst system of any of claims 1 through 8; (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. 10. The process of claim 9, wherein the vinyl terminated alkene is 1-octene 11. The process of claim 9, wherein the hydrosilylation agent comprises dimethoxymethylsilane. 12. A supported platinum catalyst system comprising: (a) a di-nitrogen ligand to complex with (b) a platinum metal ion, (c) a support and, optionally, (d) an anchoring ligand, wherein the di-nitrogen ligand comprises the formula: wherein R3 and R4 are each a carboxylic acid group; wherein the optional anchoring ligand comprises 2,2′-bipyridine-4,4′-dicarboxylic acid or 1,10-phenanthroline-5,6-dione; and the biphenyl rings can form a third ring to form a phenanthroline ring system. 13. The supported platinum catalyst system of claim 12, wherein the support comprises MgO, Al2O3, CeO2 or mixtures thereof. 14. A process comprising: (a) providing a supported catalyst system of claims 12 or 13; (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. 15. The process of claim 14, wherein the vinyl terminated alkene is 1-octene 16. The process of claim 14, wherein the hydrosilylation agent comprises dimethoxymethylsilane. |
[068] Table 2. Activity and total Pt recovery (by XPS) of Pt LCSCs. [a] Reaction condition: T = 70 °C, t = 30 min, 30 mg catalyst, 6 mmol 1, 5 mmol 2, and 3 mL toluene. [b] XPS Pt recovery was calculated based on Pt:Ce ratio compared with the fresh catalyst. [c] Reaction condition: T = 60 °C, t = 20 min, 15 mg catalyst, 3 mmol 1, 2.5 mmol 2, and 1.5 mL toluene. [d] Complete conversion of 2 was achieved in this reaction. [069] 2. Enhancing recyclability of Pt-DPTZ/CeO 2 by combination with another ligand [070] An effort to improve active site recyclability of Pt-DPTZ SACs by mixing DPTZ with another ligand was undertaken. The mixing ligand should be soluble in 1- butanol, the only solvent found to dissolve DPTZ and H 2 PtCl 6 · 6H 2 O simultaneously. BPhen was chosen over C9BP for this study because when used alone, BPhen stabilizes Pt better than C9BP according to Table 2. This is potentially due to the benzene rings on BPhen offering stronger van der Waals interaction with CeO 2 than alkyl chains on C9BP. Besides, the phenanthroline ring on BPhen is more rigid than the bi-pyridyl ring on C9BP, possibly providing a more favorable pocket for Pt binding. The synthesis procedure was adapted from the original Pt-DPTZ/CeO 2 recipe, 77 with a fraction of DPTZ replaced by BPhen. Two BPhen:DPTZ molar ratios: 2:1 and 1:2 were tested. The former does not create active hydrosilylation catalyst, so focus was on the latter, referred as Pt-BPhen+DPTZ/CeO 2 . [071] Pt-Bphen+DPTZ/CeO 2 exhibits significantly improved reusability over Pt-DPTZ/CeO 2 , as it only shows minimal activity drop in the first three cycles (81% yield to 73%, Figure 5), while the product yield decreases quickly on Pt-DPTZ/CeO 2 once the conversion of 2 drops below 100%, due to active site leaching. 78 Pt recovery percentage after the first cycle is improved as well (86% compared with 62%, Table 2). It was recognized that Pt-BPhen+DPTZ/CeO 2 was not as active as Pt-DPTZ/CeO 2 (lower yield and TON per Pt under identical reaction conditions), but the difference is within a factor of three. In practice, one can compensate for lower activity by using more catalyst, but active site leaching is more challenging, especially for expensive noble metals. Therefore, from a practical perspective, significantly enhanced reusability is more valuable. For the hydrosilylation of epoxy-containing alkene (the reaction in Scheme 3), Pt-BPhen+DPTZ/CeO 2 shows similar selectivity (63%) with Pt-DPTZ/CeO 2 (71%) at 100% silane conversion (80 °C, 100 min), 78 demonstrating desired stronger tolerance towards unstable groups than the Karstedt catalyst (~ 50% selectivity). 42, 78 These results indicate that the mixed-ligand method offers a valid approach to alleviate the active site leaching problem. This strategy also provides another layer of tunability to the Pt sites as one can change catalyst properties by varying either ligand and the molar ratio between the two ligands. [072] Scheme 3. Hydrosilylation reaction between 4-vinyl-1-cyclohexane 1,2- epoxide and trimethoxysilane. [073] Post-reaction XPS shows that on Pt-BPhen+DPTZ, only a small fraction of Pt are the active sites. According to Table 2, total Pt leaching is significant after three cycles (23% total Pt recovery). Nevertheless, the activity remains almost constant in Figure 5. This implies that the main active sites are retained, and leached Pt contribute little to the activity. Figure 2 and 6 show that fresh Pt-BPhen+DPTZ/CeO 2 has predominately Pt 2+ species. After the first cycle, Pt 4f peak shifts to slightly higher BE and the peak widens. Fitting reveals that some Pt 2+ are converted into Pt (2+δ)+ (Figure 6, Table 3). After three cycles, both BE and FWHM of Pt 4f peak change back to values similar with the fresh catalyst, and the peak can again be described with a single Pt 2+ component. These results indicate that, the Pt 2+ on fresh Pt-BPhen+DPTZ/CeO 2 represents multiple species of similar oxidation states. During 3 reaction cycles, some are converted into Pt (2+δ)+ first and then leached away. Only a small fraction are highly stable, remaining on CeO 2 with unchanged oxidation state. However, they are much more catalytically active than other species, and hence the catalyst shows good reusability overall. Table 3 and Figure 7 show that the decrease in Cl:Pt ratio after the reaction, which has been linked with Pt activation, 78 is observed on Pt- BPhen+DPTZ/CeO 2 . N:Pt ratio does not decrease (Table 3, Figure 8), highlighting the strong binding between Pt and the bidentate N pockets. It was also discovered that treating Pt-BPhen+DPTZ/CeO 2 with only 2 in toluene (without 1) at 70 °C leads to almost complete loss of Pt, N, Cl (Figures 9-11 respectively) and activity. Therefore, despite the main active Pt 2+ sites being highly recyclable under reaction conditions, interacting with silane without alkene induces complete leaching of Pt complexes. [074] Table 3. Changes in relative Pt concentrations of various oxidation states, N : Pt ratio, and Cl : Pt ratio on Pt-PDO/CeO 2 and Pt-BPhen+DPTZ/CeO 2 [a] Relative concentration of a Pt component on a sample was calculated based on the peak area from fittings (normalized to Ce 3d area of the same sample). For each catalyst, the total Pt 4f peak area of its fresh form was defined as 1. [075] 3. Using bidentate N-based ligands as “anchoring ligands” [076] The third strategy explored was to use a bidentate N-based ligand to modify oxide supports for Pt-DPTZ LCSCs. The synthesis procedure includes two steps: an “anchoring” ligand was first deposited onto an oxide to form a ligand-modified oxide. Then, Pt-DPTZ SACs were synthesized using a usual procedure, 77 with the anchoring- ligand-modified oxide as the support. Not to be limited by theory, it was hypothesized that the ligand-modified supports can enhance catalyst reusability because the anchoring ligand can offer stronger interactions with Pt than surface O from pristine oxides. The concept was tested using PDO and 4,4’-BPDCA as anchoring ligands on both CeO 2 and MgO (with similar surface area). The successful deposition of the anchoring ligand after the first step is verified by XPS N 1s peak area analysis (Figure 12), with higher loading on CeO 2 than on MgO. Pt 4f XPS of both CeO 2 -supported catalysts show predominantly Pt 2+ (Figure 13), as on pristine CeO 2 . 77 On both MgO-supported catalysts, the Pt 4f peak is wider and more asymmetric (low-binding-energy tail), compared to the CeO 2 catalysts, and fitting shows a small fraction of Pt 0 (Figure 13), likely from small amount of Pt nanoparticles, which is not observed with Pt-DPTZ on pristine MgO. 77 [077] The activity and Pt recyclability of these catalysts are reported in Table 4. The enhancement in Pt recyclability by the anchoring ligand is clearly observed on both supports, as Pt recovery increases on ligand-modified supports compared with pristine supports. Meanwhile, activity drops, the extent of which varies. Despite the activity loss, Table 4 shows that when the proper anchoring ligand and support are used (PDO and CeO 2 ), this strategy can create Pt-DPTZ LCSCs with significantly improved Pt recyclability (from 62% to 82%) while maintaining acceptable activity (68% yield at 70 °C for 30 min). Therefore, the anchoring ligand method is a promising approach. Pt recyclability is better on CeO 2 than on MgO, likely due to the higher anchoring ligand coverage CeO 2 (Figure 12). [078] Table 4. Activity and total Pt recovery (after 1 reaction cycle) of Pt- DPTZ SACs supported on anchoring-ligand-modified oxides [a] Reaction condition: T = 70 °C, t = 30 min, 30 mg catalyst, 6 mmol 1, 5 mmol 2, and 3 mL toluene. [b] Reaction condition: T = 75 °C, t = 120 min, 30 mg catalyst, 6 mmol 1, 5 mmol 2, and 3 mL toluene. [c] Complete conversion of 2 was achieved in these reactions. [d] Data on Pt-DPTZ SACs were previously published in reference 78. [079] It was noted that in some cases, the activity loss with the anchoring ligand is too significant. For example, 4,4’-BPDCA leads to complete deactivation of Pt-DPTZ SACs on CeO 2 . 5,5’-BPDCA, another ligand with the same functional groups but at different positions (Figure 14a), does the same. Control experiment shows that modifying CeO 2 with trifluoroacetic acid (Figure 14b), a ligand with a −COOH group but without the bidentate N pocket to anchor Pt-DPTZ, does not completely deactivate the catalyst. Consequently, the deactivation cannot be simply attributed to −COOH groups occupying certain catalytically relevant sites on CeO 2 , such as oxygen defects. Not to be limited by theory, it is suspected that the deactivation might be related to strong interactions between −COOH groups and CeO 2 forcing BPDCA to stand up, pushing Pt away from the support. The loss of Pt-support interaction may impact the electronic structure of Pt enough to deactivate the site. It has been demonstrated previously that surface O temporarily detach from Pt during catalysis, acting as “reversible leaving groups,” 78 so the lack of Pt-support binding may also reduce the number of leaving groups, so that the Pt is over-coordinated. The sensitivity of the metal center to the local coordination environment is a topic of ongoing study and interest. [080] Conclusions [081] A series of ligand-coordinated supported Pt hydrosilylation catalysts with various bidentate N-based ligands, designed to improve catalyst recyclability over previous Pt-DPTZ SACs are reported. These heterogeneous catalysts mostly contain highly dispersed Pt 2+ sites, and are active for alkene hydrosilylation under mild conditions with high selectivity. It has been demonstrated there are three approaches to alleviate the active site leaching problem on the original Pt-DPTZ SACs. First, by replacing DPTZ with a ligand containing additional functional groups that offer interactions with oxide supports, two active Pt hydrosilylation catalysts in Pt- BPhen/CeO 2 and Pt-C9BP/CeO 2 were developed. In addition, a material was discovered, Pt-4’4-BPDCA/CeO 2 , which can recycle Pt much more effectively but lacks catalytic activity. Second, it was discovered that mixing DPTZ with BPhen leads to a highly reusable catalyst, Pt-BPhen+DPTZ/CeO 2 , which shows only 10% activity loss after three reaction cycles, due to a Pt 2+ species that is highly active and stable, despite accounting for only a small fraction of total Pt. Finally, it was demonstrated that modifying oxide supports with an anchoring ligand, either PDO or 4’4-BPDCA, enhances Pt recyclability on Pt-DPTZ SACs supported on either CeO 2 or MgO. All three strategies are promising to enhance reusability of supported Pt-ligand single-atom hydrosilylation catalysts, while maintaining high activity and selectivity. Meanwhile, new development in synthesis methods reported here also expands future opportunities to fine-tune metal centers in these catalysts towards desired properties. [082] References [083] 1. Sommer, L.; Pietrusza, E.; Whitmore, F., Peroxide-catalyzed addition of trichlorosilane to 1-octene. J. Am. Chem. Soc.1947, 69, 188-188. [084] 2. Pierce, O. R.; Kim, Y. K., Fluorosilicones as high temperature elastomers. Rubber Chem. Technol.1971, 44, 1350-1362. [085] 3. Marciniec, B.; Walczuk, E.; Blazejewska-Chadyniak, P.; Chadyniak, D.; Kujawa-Welten, M.; Krompiec, S.; Auner, N.; Weiss, J., Organosilicon Chemistry V–From Molecules to Materials. Wiley VCH, Weinheim 2003. [086] 4. Morita, Y.; Tajima, S.; Suzuki, H.; Sugino, H., Thermally initiated cationic polymerization and properties of epoxy siloxane. J. Appl. Polym. Sci.2006, 100, 2010-2019. [087] 5. Beyou, E.; Babin, P.; Bennetau, B.; Dunogues, J.; Teyssie, D.; Boileau, S., 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. [088] 6. Iojoiu, C.; Abadie, M. J.; Harabagiu, V.; Pinteala, M.; Simionescu, B. C., Synthesis and photocrosslinking of benzyl acrylate substituted polydimethylsiloxanes. Eur. Polym. J.2000, 36, 2115-2123. [089] 7. Li, Z.; Qin, J.; Yang, Z.; Ye, C., Synthesis and structural characterization of a new polysiloxane with second‐order nonlinear optical effect. J. Appl. Polym. Sci.2004, 94, 769-774. [090] 8. Sellinger, A.; Laine, R. M.; Chu, V.; Viney, C., Palladium‐and platinum‐catalyzed coupling reactions of allyloxy aromatics with hydridosilanes and hydridosiloxanes: Novel liquid crystalline/organosilane materials. J. Polym. Sci., Part A: Polym. Chem.1994, 32, 3069-3089. [091] 9. Drazkowski, D. B.; Lee, A.; Haddad, T. S.; Cookson, D. J., Chemical substituent effects on morphological transitions in styrene−butadiene−styrene triblock copolymer grafted with polyhedral oligomeric silsesquioxanes. Macromolecules 2006, 39, 1854-1863. [092] 10. Tuchbreiter, A.; Werner, H.; Gade, L. H., “A posteriori” modification of carbosilane dendrimers and dendrons: their activation in core and branch positions. Dalton Trans.2005, 1394-1402. [093] 11. Maciejewski, H.; Wawrzyńczak, A.; Dutkiewicz, M.; Fiedorow, R., Silicone waxes—synthesis via hydrosilylation in homo-and heterogeneous systems. J. Mol. Catal. A: Chem.2006, 257, 141-148. [094] 12. Troegel, D.; Stohrer, J., 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. [095] 13. Marciniec, B., Hydrosilylation: a comprehensive review on recent advances; Springer Science & Business Media, 2008; Vol.1. [096] 14. Ganicz, T.; Pakuła, T.; Stańczyk, W. A., Novel liquid crystalline resins based on MQ siloxanes. J. Organomet. Chem.2006, 691, 5052-5055. [097] 15. Boury, B.; Corriu, R. J.; Leclercq, D.; Mutin, P. H.; Planeix, J. M.; Vioux, A., Poly (vinylsilane): a precursor to silicon carbide. 1. Preparation and characterization. Organometallics 1991, 10, 1457-1461. [098] 16. Mori, A.; Sato, H.; Mizuno, K.; Hiyama, T.; Shintani, K.; Kawakami, Y., A facile preparation and polymerization of 1, 1-difunctionalized disiloxanes. Chem. Lett.1996, 25, 517-518. [099] 17. O'brien, M. J., Polyether siloxane copolymer network compositions. US Patent 6,531,540: 2003. [0100] 18. Herzig, C.; Deubzer, B.; Huettner, D., Siloxane copolymers containing alkenyl groups, their preparation and use. US Patent 5,241,034: 1993. [0101] 19. Jyono, H.; Odaka, H.; Ito, H.; Iwakiri, H., Curable composition. US Patent 6,444,775: 2002. [0102] 20. Watabe, T.; Matsumoto, T.; Onoguchi, T.; Tsuruoka, K., Room temperature-setting compositions. US Patent 6,207,766: 2001. [0103] 21. Jerschow, P., Silicone elastomers; Smart Publications, 2001; Vol. 137. [0104] 22. Morris, R. H., Asymmetric hydrogenation, transfer hydrogenation and hydrosilylation of ketones catalyzed by iron complexes. Chem. Soc. Rev. 2009, 38, 2282-2291. [0105] 23. Langlotz, B. K.; Wadepohl, H.; Gade, L. H., Chiral bis (pyridylimino) isoindoles: A highly modular class of pincer ligands for enantioselective catalysis. Angew. Chem. Int. Ed.2008, 47, 4670-4674. [0106] 24. Bart, S. C.; Lobkovsky, E.; Chirik, P. J., 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, 13794-13807. [0107] 25. Vankelecom, I.; Jacobs, P., Dense organic catalytic membranes for fine chemical synthesis. Catal. Today 2000, 56, 147-157. [0108] 26. Xue, M.; Li, J.; Peng, J.; Bai, Y.; Zhang, G.; Xiao, W.; Lai, G., Effect of triarylphosphane ligands on the rhodium‐catalyzed hydrosilylation of alkene. Appl. Organomet. Chem.2014, 28, 120-126. [0109] 27. Igarashi, M.; Matsumoto, T.; Kobayashi, T.; Sato, K.; Ando, W.; Shimada, S.; Hara, M.; Uchida, H., Ir-catalyzed hydrosilylation reaction of allyl acetate with octakis (dimethylsiloxy) octasilsesquioxane and related hydrosilanes. J. Organomet. Chem.2014, 752, 141-146. [0110] 28. Dong, H.; Jiang, Y.; Berke, H., Rhenium-mediated dehydrogenative silylation and highly regioselective hydrosilylation of nitrile substituted olefins. J. Organomet. Chem.2014, 750, 17-22. [0111] 29. Wu, J. Y.; Stanzl, B. N.; Ritter, T., A strategy for the synthesis of well-defined iron catalysts and application to regioselective diene hydrosilylation. J. Am. Chem. Soc.2010, 132, 13214-13216. [0112] 30. Glaser, P. B.; Tilley, T. D., Catalytic hydrosilylation of alkenes by a ruthenium silylene complex. Evidence for a new hydrosilylation mechanism. J. Am. Chem. Soc.2003, 125, 13640-13641. [0113] 31. Nozakura, S.; Konotsune, S., Cyanoethylation of Trichlorosilane. II. α-Addition. Bull. Chem. Soc. Jpn.1956, 29, 326-331. [0114] 32. Bareille, L.; Becht, S.; Cui, J. L.; Le Gendre, P.; Moïse, C., First Titanium-Catalyzed a nti-1, 4-Hydrosilylation of Dienes. Organometallics 2005, 24, 5802-5806. [0115] 33. Harder, S.; Brettar, J., Rational Design of a Well‐Defined Soluble Calcium Hydride Complex. Angew. Chem. Int. Ed.2006, 45, 3474-3478. [0116] 34. Leich, V.; Spaniol, T. P.; Maron, L.; Okuda, J., Hydrosilylation catalysis by an earth alkaline metal silyl: synthesis, characterization, and reactivity of bis (triphenylsilyl) calcium. Chem. Commun.2014, 50, 2311-2314. [0117] 35. Speier, J. L.; Webster, J. A.; Barnes, G. H., 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. [0118] 36. Karstedt, B., Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes. US Patent 3,775,452: 1973. [0119] 37. Galeandro-Diamant, T.; Zanota, M.-L.; Sayah, R.; Veyre, L.; Nikitine, C.; de Bellefon, C.; Marrot, S.; Meille, V.; Thieuleux, C., Platinum nanoparticles in suspension are as efficient as Karstedt's complex for alkene hydrosilylation. Chem. Commun.2015, 51, 16194-16196. [0120] 38. Chauhan, B. P.; Rathore, J. S., Regioselective Synthesis of Multifunctional Hybrid Polysiloxanes Achieved by Pt−Nanocluster Catalysis. J. Am. Chem. Soc.2005, 127, 5790-5791. [0121] 39. Bai, Y.; Zhang, S.; Deng, Y.; Peng, J.; Li, J.; Hu, Y.; Li, X.; Lai, G., 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. [0122] 40. Stein, J.; Lewis, L.; Gao, Y.; Scott, R., 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. [0123] 41. Meister, T. K.; Riener, K.; Gigler, P.; Stohrer, J. r.; Herrmann, W. A.; Kühn, F. E., Platinum Catalysis Revisited - Unraveling Principles of Catalytic Olefin Hydrosilylation. ACS Catal.2016, 6, 1274-1284. [0124] 42. Markó, I. E.; Stérin, S.; Buisine, O.; Mignani, G.; Branlard, P.; Tinant, B.; Declercq, J.-P., Selective and efficient platinum (0)-carbene complexes as hydrosilylation catalysts. Science 2002, 298, 204-206. [0125] 43. Markó, I. E.; Sterin, S.; Buisine, O.; Berthon, G.; Michaud, G.; Tinant, B.; Declercq, J. P., Highly Active and Selective Platinum(0)‐Carbene Complexes. Efficient, Catalytic Hydrosilylation of Functionalised Olefins. Adv. Synth. Catal.2004, 346, 1429-1434. [0126] 44. Bernhammer, J. C.; Huynh, H. V., Platinum (II) complexes with thioether-functionalized benzimidazolin-2-ylidene ligands: Synthesis, structural characterization, and application in hydroelementation reactions. Organometallics 2013, 33, 172-180. [0127] 45. Dunsford, J. J.; Cavell, K. J.; Kariuki, B., Expanded ring N- heterocyclic carbene complexes of zero valent platinum dvtms (divinyltetramethyldisiloxane): Highly efficient hydrosilylation catalysts. J. Organomet. Chem.2011, 696, 188-194. [0128] 46. Taige, M. A.; Ahrens, S.; Strassner, T., Platinum (II)-bis-(N- heterocyclic carbene) complexes: synthesis, structure and catalytic activity in the hydrosilylation of alkenes. J. Organomet. Chem.2011, 696, 2918-2927. [0129] 47. Marciniec, B.; Posała, K.; Kownacki, I.; Kubicki, M.; Taylor, R., New Bis (dialkynyldisiloxane) triplatinum (0) cluster: synthesis, structure, and catalytic activity in olefin‐hydrosilylation reactions. ChemCatChem 2012, 4, 1935-1937. [0130] 48. Downing, C. M.; Kung, H. H., Diethyl sulfide stabilization of platinum-complex catalysts for hydrosilylation of olefins. Catal. Commun. 2011, 12, 1166-1169. [0131] 49. Sabourault, N.; Mignani, G.; Wagner, A.; Mioskowski, C., Platinum oxide (PtO 2 ): a potent hydrosilylation catalyst. Org. Lett.2002, 4, 2117-2119. [0132] 50. Chen, Y. J.; Ji, S. F.; Sun, W. M.; Chen, W. X.; Dong, J. C.; Wen, J. F.; Zhang, J.; Li, Z.; Zheng, L. R.; Chen, C.; Peng, Q.; Wang, D. S.; Li, Y. D., Discovering Partially Charged Single-Atom Pt for Enhanced Anti-Markovnikov Alkene Hydrosilylation. J. Am. Chem. Soc.2018, 140, 7407-7410. [0133] 51. Zhu, Y.; Cao, T.; Cao, C.; Luo, J.; Chen, W.; Zheng, L.; Dong, J.; Zhang, J.; Han, Y.; Li, Z.; Chen, C.; Peng, Q.; Wang, D.; Li, Y., 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. [0134] 52. Cui, X.; Junge, K.; Dai, X.; Kreyenschulte, C.; Pohl, M.-M.; Wohlrab, S.; Shi, F.; Brückner, A.; Beller, M., Synthesis of Single Atom Based Heterogeneous Platinum Catalysts: High Selectivity and Activity for Hydrosilylation Reactions. ACS Central Science 2017, 3, 580-585. [0135] 53. Mantovani, K. M.; Stival, J. F.; Wypych, F.; Bach, L.; Zamora, P. G. P.; Rocco, M. L.; Nakagaki, S., Unusual catalytic activity after simultaneous immobilization of two metalloporphyrins on hydrozincite/nanocrystalline anatase. J. Catal.2017, 352, 442-451. [0136] 54. Rimoldi, M.; Fodor, D.; van Bokhoven, J. A.; Mezzetti, A., A stable 16-electron iridium(III) hydride complex grafted on SBA-15: a single-site catalyst for alkene hydrogenation. Chem. Comm.2013, 49, 11314-11316. [0137] 55. Xu, W.; Li, Y.; Yu, B.; Yang, J.; Zhang, Y.; Chen, X.; Zhang, G.; Gao, Z., Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction. J. Solid State Chem. 2015, 221, 208-215. [0138] 56. Chen, L.; Rangan, S.; Li, J.; Jiang, H.; Li, Y., A molecular Pd (II) complex incorporated into a MOF as a highly active single-site heterogeneous catalyst for C–Cl bond activation. Green Chemistry 2014, 16, 3978-3985. [0139] 57. Huang, Z.; Gu, X.; Cao, Q.; Hu, P.; Hao, J.; Li, J.; Tang, X., Catalytically Active Single‐Atom Sites Fabricated from Silver Particles. Angew. Chem. 2012, 124, 4274-4279. [0140] 58. 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. [0141] 59. Chen, Y. X.; Huang, Z. W.; Ma, Z.; Chen, J. M.; Tang, X. F., Fabrication, characterization, and stability of supported single-atom catalysts. Catalysis Science & Technology 2017, 7, 4250-4258. [0142] 60. Vilé, G.; Albani, D.; Nachtegaal, M.; Chen, Z.; Dontsova, D.; Antonietti, M.; López, N.; Pérez‐Ramírez, J., A Stable Single‐Site Palladium Catalyst for Hydrogenations. Angew. Chem. Int. Ed.2015, 54, 11265-11269. [0143] 61. Xu, W.; Yu, B.; Zhang, Y.; Chen, X.; Zhang, G.; Gao, Z., Single- site SBA-15 supported zirconium catalysts. Synthesis, characterization and toward cyanosilylation reaction. Appl. Surf. Sci.2015, 325, 227-234. [0144] 62. Ji, P.; Manna, K.; Lin, Z.; Urban, A.; Greene, F. X.; Lan, G.; Lin, W., Single-Site Cobalt Catalysts at New Zr8 (μ2-O)8 (μ2-OH)4 Metal-Organic Framework Nodes for Highly Active Hydrogenation of Alkenes, Imines, Carbonyls, and Heterocycles. J. Am. Chem. Soc.2016, 138, 12234-12242. [0145] 63. Schweitzer, N. M.; Hu, B.; Das, U.; Kim, H.; Greeley, J.; Curtiss, L. A.; Stair, P. C.; Miller, J. T.; Hock, A. S., Propylene Hydrogenation and Propane Dehydrogenation by a Single-Site Zn2+ on Silica Catalyst. ACS Catal. 2014, 4, 1091- 1098. [0146] 64. Sohn, H.; Camacho-Bunquin, J.; Langeslay, R.; Ignacio-de Leon, P.; Niklas, J.; Poluektov, O.; Liu, C.; Connell, J.; Yang, D.; Kropf, J., Isolated, well- defined organovanadium (III) on silica: single-site catalyst for hydrogenation of alkenes and alkynes. Chem. Commun.2017. [0147] 65. Qiao, B.; Wang, A.; Yang, X.; Allard, L. F.; Jiang, Z.; Cui, Y.; Liu, J.; Li, J.; Zhang, T., Single-atom catalysis of CO oxidation using Pt1/FeOx. Nature chemistry 2011, 3, 634-641. [0148] 66. Li, Z.; Ji, S.; Liu, Y.; Cao, X.; Tian, S.; Chen, Y.; Niu, Z.; Li, Y., Well-Defined Materials for Heterogeneous Catalysis: From Nanoparticles to Isolated Single-Atom Sites. Chem. Rev.2019. [0149] 67. DeRita, L.; Dai, S.; Lopez-Zepeda, K.; Pham, N.; Graham, G. W.; Pan, X.; Christopher, P., Catalyst Architecture for Stable Single Atom Dispersion Enables Site-Specific Spectroscopic and Reactivity Measurements of CO Adsorbed to Pt Atoms, Oxidized Pt Clusters, and Metallic Pt Clusters on TiO 2 . J. Am. Chem. Soc.2017, 139, 14150-14165. [0150] 68. Liu, J., Catalysis by Supported Single Metal Atoms. ACS Catal. 2017, 7, 34-59. [0151] 69. Cui, X.; Li, W.; Ryabchuk, P.; Junge, K.; Beller, M., Bridging homogeneous and heterogeneous catalysis by heterogeneous single-metal-site catalysts. Nat. Catal.2018, 1, 385-397. [0152] 70. Liu, L.; Meira, D. M.; Arenal, R.; Concepcion, P.; Puga, A. V.; Corma, A., Determination of the Evolution of Heterogeneous Single Metal Atoms and Nanoclusters under Reaction Conditions: Which Are the Working Catalytic Sites? ACS Catal.2019, 10626-10639. [0153] 71. Skomski, D.; Tempas, C. D.; Cook, B. J.; Polezhaev, A. V.; Smith, K. A.; Caulton, K. G.; Tait, S. L., Two- and Three-Electron Oxidation of Single-Site Vanadium Centers at Surfaces by Ligand Design. J. Am. Chem. Soc. 2015, 137, 7898- 7902. [0154] 72. Skomski, D.; Tempas, C. D.; Bukowski, G. S.; Smith, K. A.; Tait, S. L., Redox-active on-surface polymerization of single-site divalent cations from pure metals by a ketone-functionalized phenanthroline. J. Chem. Phys.2015, 142, 101913. [0155] 73. Skomski, D.; Tempas, C. D.; Smith, K. A.; Tait, S. L., Redox- Active On-Surface Assembly of Metal-Organic Chains with Single-Site Pt(II). J. Am. Chem. Soc.2014, 136, 9862-9865. [0156] 74. Tempas, C. D.; Skomski, D.; Cook, B. J.; Le, D.; Smith, K. A.; Rahman, T. S.; Caulton, K. G.; Tait, S. L., Redox Isomeric Surface Structures Are Preferred over Odd-Electron Pt1+. Chem. Eur. J.2018, 24, 15852-15858. [0157] 75. Williams, C. G.; Wang, M.; Skomski, D.; Tempas, C. D.; Kesmodel, L. L.; Tait, S. L., Metal-Ligand Complexation through Redox Assembly at Surfaces Characterized by Vibrational Spectroscopy. J. Phys. Chem. C 2017. [0158] 76. Morris, T. W.; Huerfano, I. J.; Wang, M.; Wisman, D. L.; Cabelof, A. C.; Din, N. U.; Tempas, C. D.; Le, D.; Polezhaev, A. V.; Rahman, T. S.; Caulton, K. G.; Tait, S. L., Multi-electron Reduction Capacity and Multiple Binding Pockets in Metal–Organic Redox Assembly at Surfaces. Chem. Eur. J.2019, 25, 5565-5573. [0159] 77. Chen, L.; Sterbinsky, G. E.; Tait, S. L., Synthesis of platinum single-site centers through metal-ligand self-assembly on powdered metal oxide supports. J. Catal.2018, 365, 303-312. [0160] 78. Chen, L.; Ali, I. S.; Sterbinsky, G. E.; Gamler, J. T. L.; Skrabalak, S. E.; Tait, S. L., Alkene Hydrosilylation on Oxide-Supported Pt-Ligand Single-Site Catalysts. ChemCatChem 2019, 11, 2843-2854. [0161] 79. Chen, L.; Agrawal, V.; Tait, S. L., Sulfate promotion of selective catalytic reduction of nitric oxide by ammonia on ceria. Catalysis Science & Technology 2019, 9, 1802-1815. [0162] Although the present invention has been described with reference to preferred embodiments, persons skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. All references cited throughout the specification, including those in the background, are incorporated herein in their entirety. Those skilled in the art will recognize, or be able to ascertain, using no more than routine experimentation, many equivalents to specific embodiments of the invention described specifically herein. Such equivalents are intended to be encompassed in the scope of the following claims.