Selective photosynthesis of Z-olefins through crystalline metal-organic cage-initiated expeditious cascade reactions

Abstract

The semi-hydrogenation of alkyne to form Z-olefins with high conversion and high selectivity is still a huge challenge in the chemical industry. Moreover, flammable and explosive hydrogen as the common hydrogen source of this reaction increases the cost and danger of industrial production. Herein, we connect the photocatalytic hydrogen evolution reaction and the semi-hydrogenation reaction of alkynes in series and successfully realize the high selective production of Z-alkenes using low-cost, safe, and green water as the proton source. Before the cascade reaction, a series of isomorphic metal–organic cage catalysts (Co_xZn_8−xL₆, x = 0, 3, 4, 5, and 8) are designed and synthesized to improve the yield of the photocatalytic hydrogen production. Among them, Co₅Zn₃L₆ shows the highest photocatalytic activity, with a H₂ generation rate of 8.81 mmol g⁻¹ h⁻¹. Then, Co₅Zn₃L₆ is further applied in the above tandem reaction to efficiently reduce alkynes to Z-alkenes under ambient conditions, which can reach high conversion of >98% and high selectivity of >99%, and maintain original catalytic activity after multiple cycles. This “one-pot” tandem reaction can achieve a highly selective and safe stepwise conversion from water into hydrogen into Z-olefins under mild reaction conditions.

Keywords

alkyne semi-hydrogenation / hydrogen evolution reaction / metal-organic cages / photocatalysis / Z-olefins

References

[1] Kyriakou G, Boucher MB, Jewell AD, et al. Isolated metal atom geometries as a strategy for selective heterogeneous hydrogenations. Science. 2012; 335 (6073): 1209- 1212.

[2] Riley C, Zhou S, Kunwar D, et al. Design of effective catalysts for selective alkyne hydrogenation by doping of ceria with a single-atom promotor. J Am Chem Soc. 2018; 140 (40): 12964- 12973.

[3] Zhao X, Zhou L, Zhang W, et al. Thiol treatment creates selective palladium catalysts for semihydrogenation of internal alkynes. Chem. 2018; 4 (5): 1080- 1091.

[4] Albani D, Shahrokhi M, Chen Z, et al. Selective ensembles in supported palladium sulfide nanoparticles for alkyne semi-hydrogenation. Nat Commun. 2018; 9: 2634.

[5] Farrar-Tobar RA, Weber S, Csendes Z, et al. E-selective manganese-catalyzed semihydrogenation of alkynes with H₂ directly employed or in situ-generated. ACS Catal. 2022; 12 (4): 2253- 2260.

[6] Choe K, Zheng F, Wang H, et al. Fast and selective semihydrogenation of alkynes by palladium nanoparticles sandwiched in metal-organic frameworks. Angew Chem Int Ed. 2020; 59 (9): 3650- 3657.

[7] Zhao L, Qin X, Zhang X, et al. A magnetically separable Pd single-atom catalyst for efficient selective hydrogenation of phenylacetylene. Adv Mater. 2022; 34 (20): 2110455.

[8] Park BY, Lim T, Han MS. A simple and efficient in situ generated copper nanocatalyst for stereoselective semihydrogenation of alkynes. Chem Commun. 2021; 57 (56): 6891- 6894.

[9] Oger C, Balas L, Durand T, Galano J-M. Are alkyne reductions chemo-, regio-, and stereoselective enough to provide pure (Z)-olefins in polyfunctionalized bioactive molecules? Chem Rev. 2013; 113 (3): 1313- 1350.

[10] Lee MT, Goodstein MB, Lalic G. Synthesis of isomerically pure (Z)-alkenes from terminal alkynes and terminal alkenes: silver-catalyzed hydroalkylation of alkynes. J Am Chem Soc. 2019; 141 (43): 17086- 17091.

[11] Bhadra M, Kandambeth S, Sahoo MK, Addicoat M, Balaraman E, Banerjee R. Triazine functionalized porous covalent organic framework for photo-organocatalytic E-Z isomerization of olefins. J Am Chem Soc. 2019; 141 (15): 6152- 6156.

[12] Jiang R, Ding L, Zheng C, You S-L. Iridium-catalyzed Z-retentive asymmetric allylic substitution reactions. Science. 2021; 371 (6527): 380- 386.

[13] Wang B, Lanterna AE, Scaiano JC. Mechanistic insights on the semihydrogenation of alkynes over different nanostructured photocatalysts. ACS Catal. 2021; 11 (7): 4230- 4238.

[14] Kuwahara Y, Kango H, Yamashita H. Pd nanoparticles and aminopolymers confined in hollow silica spheres as efficient and reusable heterogeneous catalysts for semihydrogenation of alkynes. ACS Catal. 2019; 9 (3): 1993- 2006.

[15] Ji S, Chen Y, Zhao S, et al. Atomically dispersed ruthenium species inside metal-organic frameworks: combining the high activity of atomic sites and the molecular sieving effect of MOFs. Angew Chem Int Ed. 2019; 58 (13): 4271- 4275.

[16] He X, He Q, Deng Y, et al. A versatile route to fabricate single atom catalysts with high chemoselectivity and regioselectivity in hydrogenation. Nat Commun. 2019; 10: 3663.

[17] Chernichenko K, Madarász Á, Pápai I, Nieger M, Leskelä M, Repo T. A frustrated-Lewis-pair approach to catalytic reduction of alkynes to cis-alkenes. Nat Chem. 2013; 5 (8): 718- 723.

[18] Wan X-K, Wang J-Q, Nan Z-A, Wang Q-M. Ligand effects in catalysis by atomically precise gold nanoclusters. Sci Adv. 2017; 3 (10): e1701823.

[19] Zheng W, Zhou Y, Li Y. PVC-NHC-Pd(0): an efficient and reusable heterogeneous catalyst for highly cis-selective semihydrogenation of alkynes using formic acid as hydrogen source. Inorg Chem Commun. 2021; 134: 109014.

[20] Belger C, Neisius NM, Plietker B. A selective Ru-catalyzed semireduction of alkynes to Z olefins under transfer-hydrogenation conditions. Chem Eur J. 2010; 16 (40): 12214- 12220.

[21] Nie R, Tao Y, Nie Y, et al. Recent advances in catalytic transfer hydrogenation with formic acid over heterogeneous transition metal catalysts. ACS Catal. 2021; 11 (3): 1071- 1095.

[22] Lv H, Qin H, Sun M, Jia F, Huang B, Liu B. Mesoporosity-enabled selectivity of mesoporous palladium-based nanocrystals catalysts in semihydrogenation of alkynes. Angew Chem Int Ed. 2021; 61 (8): e202114539.

[23] Fu S, Chen N-Y, Liu X, Shao Z, Luo S-P, Liu Q. Ligand-controlled cobalt-catalyzed transfer hydrogenation of alkynes: stereodivergent synthesis of Z- and E-alkenes. J Am Chem Soc. 2016; 138 (27): 8588- 8594.

[24] Han C, Du L, Konarova M, Qi D-C, Phillips DL, Xu J. Beyond hydrogen evolution: solar-driven, water-donating transfer hydrogenation over platinum/carbon nitride. ACS Catal. 2020; 10 (16): 9227- 9235.

[25] Zhao E, Li M, Xu B, et al. Transfer hydrogenation with a carbon-nitride-supported palladium single-atom photocatalyst and water as a proton source. Angew Chem Int Ed. 2022; 61 (40): e202207410.

[26] Yao F, Dai L, Bi J, et al. Loofah-like carbon nitride sponge towards the highly-efficient photocatalytic transfer hydrogenation of nitrophenols with water as the hydrogen source. Chem Eng J. 2022; 444: 136430.

[27] Yang Y, Jing X, Zhang J, Yang F, Duan C. Modifying electron injection kinetics for selective photoreduction of nitroarenes into cyclic and asymmetric azo compounds. Nat Commun. 2022; 13: 1940.

[28] Li M, Zhang N, Long R, Ye W, Wang C, Xiong Y. PdPt alloy nanocatalysts supported on TiO₂: maneuvering metal-hydrogen interactions for light-driven and water-donating selective alkyne semihydrogenation. Small. 2017; 13 (23): 1604173.

[29] Arcudi F, Ðorđević L, Schweitzer N, Stupp SI, Weiss EA. Selective visible-light photocatalysis of acetylene to ethylene using a cobalt molecular catalyst and water as a proton source. Nat Chem. 2022; 14 (9): 1007- 1012.

[30] Rau S, Schäfer B, Gleich D, et al. A supramolecular photocatalyst for the production of hydrogen and the selective hydrogenation of tolane. Angew Chem Int Ed. 2006; 45 (37): 6215- 6218.

[31] Lu M, Zhang M, Liu J, et al. Covalent organic framework based functional materials: important catalysts for efficient CO₂ utilization. Angew Chem Int Ed. 2022; 61 (15): e202200003.

[32] Xia Y-S, Tang M, Zhang L, et al. Tandem utilization of CO₂ photoreduction products for the carbonylation of aryl iodides. Nat Commun. 2022; 13: 2964.

[33] Ma X, Liu H, Yang W, Mao G, Zheng L, Jiang H-L. Modulating coordination environment of single-atom catalysts and their proximity to photosensitive units for boosting MOF photocatalysis. J Am Chem Soc. 2021; 143 (31): 12220- 12229.

[34] Kang X-M, Tang M-H, Yang G-L, Zhao B. Cluster/cage-based coordination polymers with tetrazole derivatives. Coord Chem Rev. 2020; 422: 213424.

[35] Zhang L, Li X-X, Lang Z-L, et al. Enhanced cuprophilic interactions in crystalline catalysts facilitate the highly selective electroreduction of CO₂ to CH₄. J Am Chem Soc. 2021; 143 (10): 3808- 3816.

[36] Xue Y, Hang X, Ding J, et al. Catalysis within coordination cages. Coord Chem Rev. 2021; 430: 213656.

[37] Fan W, Peh SB, Zhang Z, et al. Tetrazole-functionalized zirconium metal-organic cages for efficient C₂H₂/C₂H₄ and C₂H₂/CO₂ separations. Angew Chem Int Ed. 2021; 60 (32): 17338- 17343.

[38] Zhu J-L, Zhang D, Ronson TK, et al. A cavity-tailored metal-organic cage entraps gases selectively in solution and the amorphous solid state. Angew Chem Int Ed. 2021; 60 (21): 11789- 11792.

[39] Luo D, Wang X-Z, Yang C, Zhou X-P, Li D. Self-assembly of chiral metal-organic tetartoid. J Am Chem Soc. 2018; 140 (1): 118- 121.

[40] Tian L, Wang C, Zhao H, et al. Rational approach to plasmonic dimers with controlled gap distance, symmetry, and capability of precisely hosting guest molecules in hotspot regions. J Am Chem Soc. 2021; 143 (23): 8631- 8638.

[41] Tang X, Chu D, Gong W, Cui Y, Liu Y. Metal-organic cages with missing linker defects. Angew Chem Int Ed. 2021; 60 (16): 9099- 9105.

[42] Kieffer M, Bilbeisi RA, Thoburn JD, Clegg JK, Nitschke JR. Guest binding drives host redistribution in libraries of Co^II₄L₄ cages. Angew Chem Int Ed. 2020; 59 (28): 11369- 11373.

[43] Wu K, Li K, Chen S, et al. The redox coupling effect in a photocatalytic Ru^II-Pd^II cage with TTF guest as electron relay mediator for visible-light hydrogen-evolving promotion. Angew Chem Int Ed. 2020; 59 (7): 2639- 2643.

[44] Tan C, Jiao J, Li Z, Liu Y, Han X, Cui Y. Design and assembly of a chiral metallosalen-based octahedral coordination cage for supramolecular asymmetric catalysis. Angew Chem Int Ed. 2018; 57 (8): 2085- 2090.

[45] Liu G, Zhou M, Su K, Babarao R, Yuan D, Hong M. Stabilizing the extrinsic porosity in metal-organic cages-based supramolecular framework by in situ catalytic polymerization. CCS Chem. 2021; 3 (5): 1382- 1390.

[46] Bodedla GB, Wong W-Y, Zhu X. Coupling of a new porphyrin photosensitizer and cobaloxime cocatalyst for highly efficient photocatalytic H₂ evolution. J Mater Chem A. 2021; 9 (36): 20645- 20652.

[47] Banerjee T, Haase F, Savasci G, Gottschling K, Ochsenfeld C, Lotsch BV. Single-site photocatalytic H₂ evolution from covalent organic frameworks with molecular cobaloxime co-catalysts. J Am Chem Soc. 2017; 139 (45): 16228- 16234.

[48] Huang B, Xiao L, Lu J, Zhuang L. Spatially resolved quantification of the surface reactivity of solid. Angew Chem Int Ed. 2016; 55 (21): 6239- 6243.

[49] Jafarpour M, Feizpour F, Rezaeifard A, Pourmorteza N, Breit B. Tandem photocatalysis protocol for hydrogen generation/olefin hydrogenation using Pd-g-C₃N₄-imine/TiO₂ nanoparticles. Inorg Chem. 2021; 60 (13): 9484- 9495.

[50] Jeske K, Rösler T, Belleflamme M, et al. Back cover: direct conversion of syngas to higher alcohols via tandem integration of Fischer-Tropsch synthesis and reductive hydroformylation. Angew Chem Int Ed. 2022; 61 (31): e202201004.

[51] Vermeire FH, Chung Y, Green WH. Predicting solubility limits of organic solutes for a wide range of solvents and temperatures. J Am Chem Soc. 2022; 144 (24): 10785- 10797.

[52] Mellmer MA, Sanpitakseree C, Demir B, et al. Solvent-enabled control of reactivity for liquid-phase reactions of biomass-derived compounds. Nat Catal. 2018; 1 (3): 199- 207.

[53] Gnaim S, Bauer A, Zhang H-J, et al. Cobalt-electrocatalytic HAT for functionalization of unsaturated C-C bonds. Nature. 2022; 605 (7911): 687- 695.

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