Mechanistic roles of metal- and ligand-protonated species in hydrogen evolution with [CpRh] complexes
Protonation reactions involving organometallic complexes are ubiquitous in redox chemistry and often result in the generation of reactive metal hydrides. However, some organometallic species supported by η -pentamethylcyclopentadienyl (Cp*) ligands have recently been shown to undergo ligand-centered...
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Published in | Proceedings of the National Academy of Sciences - PNAS Vol. 120; no. 21; p. e2217189120 |
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Main Authors | , , , , , , |
Format | Journal Article |
Language | English |
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United States
National Academy of Sciences
23.05.2023
Proceedings of the National Academy of Sciences |
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Abstract | Protonation reactions involving organometallic complexes are ubiquitous in redox chemistry and often result in the generation of reactive metal hydrides. However, some organometallic species supported by η
-pentamethylcyclopentadienyl (Cp*) ligands have recently been shown to undergo ligand-centered protonation by direct proton transfer from acids or tautomerization of metal hydrides, resulting in the generation of complexes bearing the uncommon η
-pentamethylcyclopentadiene (Cp*H) ligand. Here, time-resolved pulse radiolysis (PR) and stopped-flow spectroscopic studies have been applied to examine the kinetics and atomistic details involved in the elementary electron- and proton-transfer steps leading to complexes ligated by Cp*H, using Cp*Rh(bpy) as a molecular model (where bpy is 2,2'-bipyridyl). Stopped-flow measurements coupled with infrared and UV-visible detection reveal that the sole product of initial protonation of Cp*Rh(bpy) is [Cp*Rh(H)(bpy)]
, an elusive hydride complex that has been spectroscopically and kinetically characterized here. Tautomerization of the hydride leads to the clean formation of [(Cp*H)Rh(bpy)]
. Variable-temperature and isotopic labeling experiments further confirm this assignment, providing experimental activation parameters and mechanistic insight into metal-mediated hydride-to-proton tautomerism. Spectroscopic monitoring of the second proton transfer event reveals that both the hydride and related Cp*H complex can be involved in further reactivity, showing that [(Cp*H)Rh] is not necessarily an off-cycle intermediate, but, instead, depending on the strength of the acid used to drive catalysis, an active participant in hydrogen evolution. Identification of the mechanistic roles of the protonated intermediates in the catalysis studied here could inform design of optimized catalytic systems supported by noninnocent cyclopentadienyl-type ligands. |
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AbstractList | Protonation reactions involving organometallic complexes are ubiquitous in redox chemistry and often result in the generation of reactive metal hydrides. However, some organometallic species supported by η
-pentamethylcyclopentadienyl (Cp*) ligands have recently been shown to undergo ligand-centered protonation by direct proton transfer from acids or tautomerization of metal hydrides, resulting in the generation of complexes bearing the uncommon η
-pentamethylcyclopentadiene (Cp*H) ligand. Here, time-resolved pulse radiolysis (PR) and stopped-flow spectroscopic studies have been applied to examine the kinetics and atomistic details involved in the elementary electron- and proton-transfer steps leading to complexes ligated by Cp*H, using Cp*Rh(bpy) as a molecular model (where bpy is 2,2'-bipyridyl). Stopped-flow measurements coupled with infrared and UV-visible detection reveal that the sole product of initial protonation of Cp*Rh(bpy) is [Cp*Rh(H)(bpy)]
, an elusive hydride complex that has been spectroscopically and kinetically characterized here. Tautomerization of the hydride leads to the clean formation of [(Cp*H)Rh(bpy)]
. Variable-temperature and isotopic labeling experiments further confirm this assignment, providing experimental activation parameters and mechanistic insight into metal-mediated hydride-to-proton tautomerism. Spectroscopic monitoring of the second proton transfer event reveals that both the hydride and related Cp*H complex can be involved in further reactivity, showing that [(Cp*H)Rh] is not necessarily an off-cycle intermediate, but, instead, depending on the strength of the acid used to drive catalysis, an active participant in hydrogen evolution. Identification of the mechanistic roles of the protonated intermediates in the catalysis studied here could inform design of optimized catalytic systems supported by noninnocent cyclopentadienyl-type ligands. Protonation reactions involving organometallic complexes are ubiquitous in redox chemistry and often result in the generation of reactive metal hydrides. However, some organometallic species supported by η5-pentamethylcyclopentadienyl (Cp*) ligands have recently been shown to undergo ligand-centered protonation by direct proton transfer from acids or tautomerization of metal hydrides, resulting in the generation of complexes bearing the uncommon η4-pentamethylcyclopentadiene (Cp*H) ligand. Here, time-resolved pulse radiolysis (PR) and stopped-flow spectroscopic studies have been applied to examine the kinetics and atomistic details involved in the elementary electron- and proton-transfer steps leading to complexes ligated by Cp*H, using Cp*Rh(bpy) as a molecular model (where bpy is 2,2'-bipyridyl). Stopped-flow measurements coupled with infrared and UV-visible detection reveal that the sole product of initial protonation of Cp*Rh(bpy) is [Cp*Rh(H)(bpy)]+, an elusive hydride complex that has been spectroscopically and kinetically characterized here. Tautomerization of the hydride leads to the clean formation of [(Cp*H)Rh(bpy)]+. Variable-temperature and isotopic labeling experiments further confirm this assignment, providing experimental activation parameters and mechanistic insight into metal-mediated hydride-to-proton tautomerism. Spectroscopic monitoring of the second proton transfer event reveals that both the hydride and related Cp*H complex can be involved in further reactivity, showing that [(Cp*H)Rh] is not necessarily an off-cycle intermediate, but, instead, depending on the strength of the acid used to drive catalysis, an active participant in hydrogen evolution. Identification of the mechanistic roles of the protonated intermediates in the catalysis studied here could inform design of optimized catalytic systems supported by noninnocent cyclopentadienyl-type ligands. Protonation reactions involving organometallic complexes are ubiquitous in redox chemistry and often result in the generation of reactive metal hydrides. However, some organometallic species supported by η 5 -pentamethylcyclopentadienyl (Cp*) ligands have recently been shown to undergo ligand-centered protonation by direct proton transfer from acids or tautomerization of metal hydrides, resulting in the generation of complexes bearing the uncommon η 4 -pentamethylcyclopentadiene (Cp*H) ligand. Here, time-resolved pulse radiolysis (PR) and stopped-flow spectroscopic studies have been applied to examine the kinetics and atomistic details involved in the elementary electron- and proton-transfer steps leading to complexes ligated by Cp*H, using Cp*Rh(bpy) as a molecular model (where bpy is 2,2′-bipyridyl). Stopped-flow measurements coupled with infrared and UV-visible detection reveal that the sole product of initial protonation of Cp*Rh(bpy) is [Cp*Rh(H)(bpy)] + , an elusive hydride complex that has been spectroscopically and kinetically characterized here. Tautomerization of the hydride leads to the clean formation of [(Cp*H)Rh(bpy)] + . Variable-temperature and isotopic labeling experiments further confirm this assignment, providing experimental activation parameters and mechanistic insight into metal-mediated hydride-to-proton tautomerism. Spectroscopic monitoring of the second proton transfer event reveals that both the hydride and related Cp*H complex can be involved in further reactivity, showing that [(Cp*H)Rh] is not necessarily an off-cycle intermediate, but, instead, depending on the strength of the acid used to drive catalysis, an active participant in hydrogen evolution. Identification of the mechanistic roles of the protonated intermediates in the catalysis studied here could inform design of optimized catalytic systems supported by noninnocent cyclopentadienyl-type ligands. |
Author | Henke, Wade C Blakemore, James D Grills, David C Peng, Yun Polyansky, Dmitry E Meier, Alex A Fujita, Etsuko |
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Cites_doi | 10.1002/cssc.201701559 10.1021/jacs.9b00193 10.1002/anie.198705671 10.1002/anie.201704854 10.1021/ja00423a017 10.1021/jacs.0c09363 10.1021/om00039a059 10.1016/S0022-0728(77)80143-5 10.1021/om00032a031 10.1039/C6CC00575F 10.1021/bi061980o 10.1002/chem.202103970 10.1021/ja00744a008 10.1016/S0040-4039(00)96919-3 10.1016/j.poly.2014.05.022 10.1021/ja00222a079 10.1021/om00040a001 10.1021/ja01507a011 10.1002/ange.19870990615 10.1021/cr100436k 10.1039/C8CP00977E 10.1002/1521-3765(20020215)8:4<868::AID-CHEM868>3.0.CO;2-I 10.1021/ja4093743 10.1021/ic00278a026 10.1021/ja002395s 10.1021/om00051a056 10.1039/c39920001602 10.1002/cbic.201200115 10.1016/0022-1902(56)80073-0 10.1021/acs.inorgchem.8b02160 10.1080/02603598208078100 10.1016/j.jorganchem.2020.121294 10.1021/om9709502 10.1039/C7SC05058E 10.3390/molecules23112857 10.1039/a827323z 10.1002/cphc.200800356 10.1021/ja027670k 10.1021/ar50055a001 10.1002/cber.19891221008 10.1021/acssuschemeng.8b05728 10.1021/om00037a033 10.1073/pnas.1606018113 10.1021/cs401013v 10.1021/acs.jpcb.1c08946 10.1021/om500647h 10.1021/om00012a039 10.1021/acs.organomet.1c00525 10.1021/ja01128a527 10.1021/ja00169a026 10.1021/jo9011255 10.1021/ja01504a062 10.1139/v88-234 10.1021/ar50075a002 10.1002/cssc.201701416 10.1021/acs.inorgchem.9b00371 10.1021/acs.inorgchem.7b01895 10.1021/ja983448x 10.1021/acs.organomet.7b00889 10.1021/acs.inorgchem.7b01698 |
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References | e_1_3_4_3_2 e_1_3_4_1_2 e_1_3_4_61_2 e_1_3_4_9_2 e_1_3_4_63_2 e_1_3_4_7_2 e_1_3_4_40_2 e_1_3_4_5_2 e_1_3_4_23_2 e_1_3_4_44_2 e_1_3_4_21_2 e_1_3_4_42_2 e_1_3_4_27_2 e_1_3_4_25_2 e_1_3_4_46_2 e_1_3_4_29_2 e_1_3_4_30_2 e_1_3_4_51_2 e_1_3_4_11_2 e_1_3_4_34_2 e_1_3_4_57_2 e_1_3_4_55_2 e_1_3_4_32_2 e_1_3_4_59_2 e_1_3_4_53_2 e_1_3_4_15_2 e_1_3_4_38_2 e_1_3_4_13_2 e_1_3_4_36_2 e_1_3_4_19_2 e_1_3_4_17_2 e_1_3_4_2_2 e_1_3_4_60_2 e_1_3_4_62_2 e_1_3_4_8_2 e_1_3_4_41_2 e_1_3_4_6_2 Henke W. (e_1_3_4_48_2) 2022; 28 e_1_3_4_4_2 e_1_3_4_22_2 e_1_3_4_45_2 e_1_3_4_20_2 e_1_3_4_43_2 e_1_3_4_26_2 e_1_3_4_49_2 e_1_3_4_24_2 e_1_3_4_47_2 e_1_3_4_28_2 e_1_3_4_52_2 e_1_3_4_50_2 e_1_3_4_12_2 e_1_3_4_33_2 e_1_3_4_58_2 e_1_3_4_54_2 e_1_3_4_10_2 e_1_3_4_31_2 e_1_3_4_16_2 e_1_3_4_37_2 e_1_3_4_14_2 e_1_3_4_35_2 e_1_3_4_56_2 e_1_3_4_18_2 e_1_3_4_39_2 |
References_xml | – ident: e_1_3_4_42_2 doi: 10.1002/cssc.201701559 – ident: e_1_3_4_23_2 doi: 10.1021/jacs.9b00193 – ident: e_1_3_4_25_2 doi: 10.1002/anie.198705671 – ident: e_1_3_4_11_2 doi: 10.1002/anie.201704854 – ident: e_1_3_4_3_2 doi: 10.1021/ja00423a017 – ident: e_1_3_4_24_2 doi: 10.1021/jacs.0c09363 – ident: e_1_3_4_14_2 doi: 10.1021/om00039a059 – ident: e_1_3_4_44_2 doi: 10.1016/S0022-0728(77)80143-5 – ident: e_1_3_4_5_2 doi: 10.1021/om00032a031 – ident: e_1_3_4_20_2 doi: 10.1039/C6CC00575F – ident: e_1_3_4_61_2 doi: 10.1021/bi061980o – volume: 28 year: 2022 ident: e_1_3_4_48_2 article-title: Evidence for charge delocalization in diazafluorene ligands supporting low-valent [Cp*Rh] complexes publication-title: Chem. Eur. J. doi: 10.1002/chem.202103970 contributor: fullname: Henke W. – ident: e_1_3_4_6_2 doi: 10.1021/ja00744a008 – ident: e_1_3_4_28_2 doi: 10.1016/S0040-4039(00)96919-3 – ident: e_1_3_4_38_2 doi: 10.1016/j.poly.2014.05.022 – ident: e_1_3_4_46_2 doi: 10.1021/ja00222a079 – ident: e_1_3_4_15_2 doi: 10.1021/om00040a001 – ident: e_1_3_4_4_2 doi: 10.1021/ja01507a011 – ident: e_1_3_4_26_2 doi: 10.1002/ange.19870990615 – ident: e_1_3_4_58_2 doi: 10.1021/cr100436k – ident: e_1_3_4_63_2 – ident: e_1_3_4_43_2 doi: 10.1039/C8CP00977E – ident: e_1_3_4_8_2 doi: 10.1002/1521-3765(20020215)8:4<868::AID-CHEM868>3.0.CO;2-I – ident: e_1_3_4_53_2 doi: 10.1021/ja4093743 – ident: e_1_3_4_9_2 doi: 10.1021/ic00278a026 – ident: e_1_3_4_18_2 doi: 10.1021/ja002395s – ident: e_1_3_4_27_2 doi: 10.1021/om00051a056 – ident: e_1_3_4_16_2 doi: 10.1039/c39920001602 – ident: e_1_3_4_29_2 doi: 10.1002/cbic.201200115 – ident: e_1_3_4_2_2 doi: 10.1016/0022-1902(56)80073-0 – ident: e_1_3_4_30_2 doi: 10.1021/acs.inorgchem.8b02160 – ident: e_1_3_4_50_2 doi: 10.1080/02603598208078100 – ident: e_1_3_4_62_2 – ident: e_1_3_4_31_2 doi: 10.1016/j.jorganchem.2020.121294 – ident: e_1_3_4_52_2 doi: 10.1021/om9709502 – ident: e_1_3_4_35_2 doi: 10.1039/C7SC05058E – ident: e_1_3_4_47_2 doi: 10.3390/molecules23112857 – ident: e_1_3_4_7_2 doi: 10.1039/a827323z – ident: e_1_3_4_54_2 doi: 10.1002/cphc.200800356 – ident: e_1_3_4_59_2 doi: 10.1021/ja027670k – ident: e_1_3_4_60_2 doi: 10.1021/ar50055a001 – ident: e_1_3_4_37_2 doi: 10.1002/cber.19891221008 – ident: e_1_3_4_34_2 doi: 10.1021/acssuschemeng.8b05728 – ident: e_1_3_4_13_2 doi: 10.1021/om00037a033 – ident: e_1_3_4_19_2 doi: 10.1073/pnas.1606018113 – ident: e_1_3_4_40_2 doi: 10.1021/cs401013v – ident: e_1_3_4_45_2 doi: 10.1021/acs.jpcb.1c08946 – ident: e_1_3_4_39_2 doi: 10.1021/om500647h – ident: e_1_3_4_17_2 doi: 10.1021/om00012a039 – ident: e_1_3_4_32_2 doi: 10.1021/acs.organomet.1c00525 – ident: e_1_3_4_1_2 doi: 10.1021/ja01128a527 – ident: e_1_3_4_12_2 doi: 10.1021/ja00169a026 – ident: e_1_3_4_57_2 doi: 10.1021/jo9011255 – ident: e_1_3_4_10_2 doi: 10.1021/ja01504a062 – ident: e_1_3_4_51_2 doi: 10.1139/v88-234 – ident: e_1_3_4_55_2 doi: 10.1021/ar50075a002 – ident: e_1_3_4_22_2 doi: 10.1002/cssc.201701416 – ident: e_1_3_4_36_2 doi: 10.1021/acs.inorgchem.9b00371 – ident: e_1_3_4_49_2 – ident: e_1_3_4_21_2 doi: 10.1021/acs.inorgchem.7b01895 – ident: e_1_3_4_56_2 doi: 10.1021/ja983448x – ident: e_1_3_4_33_2 doi: 10.1021/acs.organomet.7b00889 – ident: e_1_3_4_41_2 doi: 10.1021/acs.inorgchem.7b01698 |
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Snippet | Protonation reactions involving organometallic complexes are ubiquitous in redox chemistry and often result in the generation of reactive metal hydrides.... |
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SubjectTerms | 08 HYDROGEN Catalysis Design optimization energy Hydrogen evolution Intermediates Isotopic labeling Ligands Metal hydrides Metals Organometallic complexes Protonation Protons Pulse radiolysis Radioactive labeling redox chemistry stopped-flow Tautomerism |
Title | Mechanistic roles of metal- and ligand-protonated species in hydrogen evolution with [CpRh] complexes |
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