1 Ligand-Free Sub-Nanometer Metal Clusters in Catalysis
35
25. Grancha T, Ferrando-Soria J, Zhou H-C et al (2015) Postsynthetic improvement of the physical
properties in a metal-organic framework through a single crystal to single crystal transmetalation. Angew Chemie, Int Ed 54:6521–6525. https://doi.org/10.1002/anie.201501691
26. Hashmi ASK, Frost TM, Bats JW (2000) Highly selective gold-catalyzed arene synthesis. J
Am Chem Soc 122:11553–11554. https://doi.org/10.1021/ja005570d
27. Hay AS (1962) Oxidative coupling of acetylenes. ii1. J Org Chem 27:3320–3321. https://doi.
org/10.1021/jo01056a511
28. Hernández E, Bertin V, Soto J et al (2018) Catalytic reduction of nitrous oxide by the lowsymmetry pt8 cluster. J Phys Chem A 122:2209–2220. https://doi.org/10.1021/acs.jpca.7b1
1055
29. Herzing AA, Kiely CJ, Carley AF, et al (2008) Identification of active gold nanoclusters on iron
oxide supports for CO oxidation. Science (80) 321:1331 LP–1335. https://doi.org/10.1126/sci
ence.1159639
30. Ikuno T, Zheng J, Vjunov A et al (2017) Methane oxidation to methanol catalyzed by cu-oxo
clusters stabilized in nu-1000 metal-organic framework. J Am Chem Soc 139:10294–10301.
https://doi.org/10.1021/jacs.7b02936
31. Imaoka T, Akanuma Y, Haruta N et al (2017) Platinum clusters with precise numbers of atoms
for preparative-scale catalysis. Nat Commun 8:688. https://doi.org/10.1038/s41467-017-008
00-4
32. Imaoka T, Yamamoto K (2019) Wet-chemical strategy for atom-precise metal cluster catalysts.
Bull Chem Soc Jpn 92:941–948. https://doi.org/10.1246/bcsj.20190008
33. Kennedy-Smith JJ, Staben ST, Toste FD (2004) Gold(I)-catalyzed conia-ene reaction of βketoesters with alkynes. J Am Chem Soc 126:4526–4527. https://doi.org/10.1021/ja049487s
34. Leyva-Perez A (2017) Sub-nanometre metal clusters for catalytic carbon-carbon and carbonheteroatom cross-coupling reactions. Dalt Trans 46:15987–15990. https://doi.org/10.1039/
C7DT03203J
35. Leyva-Perez A, Corma A (2012) Similarities and differences between the “relativistic” triad
gold, platinum, and mercury in catalysis. Angew Chemie, Int Ed 51:614–635. https://doi.org/
10.1002/anie.201101726
36. Leyva-Perez A, Domenech-Carbo A, Corma A (2015) Unique distal size selectivity with a
digold catalyst during alkyne homocoupling. Nat Commun 6:6703. https://doi.org/10.1038/
ncomms7703
37. Leyva-Perez A, Oliver-Meseguer J, Rubio-Marques P, Corma A (2013) Water-stabilized threeand four-atom palladium clusters as highly active catalytic species in ligand-free C-C crosscoupling reactions. Angew Chemie, Int Ed 52:11554–11559. https://doi.org/10.1002/anie.201
303188
38. Liu L, Corma A (2018) Metal catalysts for heterogeneous catalysis: from single atoms to
nanoclusters and nanoparticles. Chem Rev (Washington, DC, United States) 118:4981–5079.
https://doi.org/10.1021/acs.chemrev.7b00776
39. Liu L, Zakharov DN, Arenal R et al (2018) Evolution and stabilization of subnanometric metal
species in confined space by in situ TEM. Nat Commun 9:1–10. https://doi.org/10.1038/s41
467-018-03012-6
40. Liu P, Zhao Y, Qin R, et al (2016) Photochemical route for synthesizing atomically dispersed
palladium catalysts. Science (80) 352:797 LP–800. https://doi.org/10.1126/science.aaf5251
41. Longoni G, Chini P (1976) Synthesis and chemical characterization of platinum carbonyl
dianions [Pt3(CO)6]n2- (n = .apprx.10,6,5,4,3,2,1). A new series of inorganic oligomers. J
Am Chem Soc 98:7225–7231. https://doi.org/10.1021/ja00439a020
42. Marciniec B (2008) Hydrosilylation of unsaturated carbon—heteroatom bonds
43. Marcinkowski MD, Liu J, Murphy CJ et al (2017) Selective formic acid dehydrogenation on
Pt-Cu single-atom alloys. ACS Catal 7:413–420. https://doi.org/10.1021/acscatal.6b02772
44. Mon M, Ferrando-Soria J, Grancha T et al (2016) Selective gold recovery and catalysis in a
highly flexible methionine-decorated metal-organic framework. J Am Chem Soc 138:7864–
7867. https://doi.org/10.1021/jacs.6b04635
35
25. Grancha T, Ferrando-Soria J, Zhou H-C et al (2015) Postsynthetic improvement of the physical
properties in a metal-organic framework through a single crystal to single crystal transmetalation. Angew Chemie, Int Ed 54:6521–6525. https://doi.org/10.1002/anie.201501691
26. Hashmi ASK, Frost TM, Bats JW (2000) Highly selective gold-catalyzed arene synthesis. J
Am Chem Soc 122:11553–11554. https://doi.org/10.1021/ja005570d
27. Hay AS (1962) Oxidative coupling of acetylenes. ii1. J Org Chem 27:3320–3321. https://doi.
org/10.1021/jo01056a511
28. Hernández E, Bertin V, Soto J et al (2018) Catalytic reduction of nitrous oxide by the lowsymmetry pt8 cluster. J Phys Chem A 122:2209–2220. https://doi.org/10.1021/acs.jpca.7b1
1055
29. Herzing AA, Kiely CJ, Carley AF, et al (2008) Identification of active gold nanoclusters on iron
oxide supports for CO oxidation. Science (80) 321:1331 LP–1335. https://doi.org/10.1126/sci
ence.1159639
30. Ikuno T, Zheng J, Vjunov A et al (2017) Methane oxidation to methanol catalyzed by cu-oxo
clusters stabilized in nu-1000 metal-organic framework. J Am Chem Soc 139:10294–10301.
https://doi.org/10.1021/jacs.7b02936
31. Imaoka T, Akanuma Y, Haruta N et al (2017) Platinum clusters with precise numbers of atoms
for preparative-scale catalysis. Nat Commun 8:688. https://doi.org/10.1038/s41467-017-008
00-4
32. Imaoka T, Yamamoto K (2019) Wet-chemical strategy for atom-precise metal cluster catalysts.
Bull Chem Soc Jpn 92:941–948. https://doi.org/10.1246/bcsj.20190008
33. Kennedy-Smith JJ, Staben ST, Toste FD (2004) Gold(I)-catalyzed conia-ene reaction of βketoesters with alkynes. J Am Chem Soc 126:4526–4527. https://doi.org/10.1021/ja049487s
34. Leyva-Perez A (2017) Sub-nanometre metal clusters for catalytic carbon-carbon and carbonheteroatom cross-coupling reactions. Dalt Trans 46:15987–15990. https://doi.org/10.1039/
C7DT03203J
35. Leyva-Perez A, Corma A (2012) Similarities and differences between the “relativistic” triad
gold, platinum, and mercury in catalysis. Angew Chemie, Int Ed 51:614–635. https://doi.org/
10.1002/anie.201101726
36. Leyva-Perez A, Domenech-Carbo A, Corma A (2015) Unique distal size selectivity with a
digold catalyst during alkyne homocoupling. Nat Commun 6:6703. https://doi.org/10.1038/
ncomms7703
37. Leyva-Perez A, Oliver-Meseguer J, Rubio-Marques P, Corma A (2013) Water-stabilized threeand four-atom palladium clusters as highly active catalytic species in ligand-free C-C crosscoupling reactions. Angew Chemie, Int Ed 52:11554–11559. https://doi.org/10.1002/anie.201
303188
38. Liu L, Corma A (2018) Metal catalysts for heterogeneous catalysis: from single atoms to
nanoclusters and nanoparticles. Chem Rev (Washington, DC, United States) 118:4981–5079.
https://doi.org/10.1021/acs.chemrev.7b00776
39. Liu L, Zakharov DN, Arenal R et al (2018) Evolution and stabilization of subnanometric metal
species in confined space by in situ TEM. Nat Commun 9:1–10. https://doi.org/10.1038/s41
467-018-03012-6
40. Liu P, Zhao Y, Qin R, et al (2016) Photochemical route for synthesizing atomically dispersed
palladium catalysts. Science (80) 352:797 LP–800. https://doi.org/10.1126/science.aaf5251
41. Longoni G, Chini P (1976) Synthesis and chemical characterization of platinum carbonyl
dianions [Pt3(CO)6]n2- (n = .apprx.10,6,5,4,3,2,1). A new series of inorganic oligomers. J
Am Chem Soc 98:7225–7231. https://doi.org/10.1021/ja00439a020
42. Marciniec B (2008) Hydrosilylation of unsaturated carbon—heteroatom bonds
43. Marcinkowski MD, Liu J, Murphy CJ et al (2017) Selective formic acid dehydrogenation on
Pt-Cu single-atom alloys. ACS Catal 7:413–420. https://doi.org/10.1021/acscatal.6b02772
44. Mon M, Ferrando-Soria J, Grancha T et al (2016) Selective gold recovery and catalysis in a
highly flexible methionine-decorated metal-organic framework. J Am Chem Soc 138:7864–
7867. https://doi.org/10.1021/jacs.6b04635