We employ a metal‐metal salt metathesis strategy to access low‐valent tantalum‐copper heterometallic architectures (Ta−μ2‐H2−Cu and Ta−μ3‐H2−Cu3) that emulate structural elements proposed for surface alloyed nanomaterials. Whereas cluster assembly with carbonylmetalates is well precedented, the use of the corresponding polyarene transition metal anions is underexplored, despite recognition of these highly reactive fragments as storable sources of atomic Mn−. Our application of this strategy provides structurally unique early‐late bimetallic species. These complexes incorporate bridging hydride ligands during their syntheses, the origin of which is elucidated via detailed isotopic labelling studies. Modification of ancillary ligand sterics and electronics alters the mechanism of bimetallic assembly; a trinuclear complex resulting from dinuclear C−H activation is demonstrated as an intermediate
We employ a metal‐metal salt metathesis strategy to access low‐valent tantalum‐copper heterometallic architectures (Ta−μ2‐H2−Cu and Ta−μ3‐H2−Cu3) that emulate structural elements proposed for surface alloyed nanomaterials. Whereas cluster assembly with carbonylmetalates is well precedented, the use of the corresponding polyarene transition metal anions is underexplored, despite recognition of these highly reactive fragments as storable sources of atomic Mn−. Our application of this strategy provides structurally unique early‐late bimetallic species. These complexes incorporate bridging hydride ligands during their syntheses, the origin of which is elucidated via detailed isotopic labelling studies. Modification of ancillary ligand sterics and electronics alters the mechanism of bimetallic assembly; a trinuclear complex resulting from dinuclear C−H activation is demonstrated as an intermediate
- NSF-PAR ID:
- 10471180
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 62
- Issue:
- 48
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract en route to formation of the bimetallic. Further validating the promise of this rational, bottom‐up approach, a unique tetranuclear species was synthesized, featuring a Ta centre bearing three Ta−Cu interactions. -
Calcium‐Ion Binding Mediates the Reversible Interconversion of Cis and Trans Peroxido Dicopper Coresmore » « less
Abstract Coupled dinuclear copper oxygen cores (Cu2O2) featured in type III copper proteins (hemocyanin, tyrosinase, catechol oxidase) are vital for O2transport and substrate oxidation in many organisms.
μ ‐1,2‐cis peroxido dicopper cores (C P ) have been proposed as key structures in the early stages of O2binding in these proteins; their reversible isomerization to other Cu2O2cores are directly relevant to enzyme function. Despite the relevance of such species to type III copper proteins and the broader interest in the properties and reactivity of bimetallicC P cores in biological and synthetic systems, the properties and reactivity ofC P Cu2O2species remain largely unexplored. Herein, we report the reversible interconversion ofμ ‐1,2‐trans peroxido (T P ) andC P dicopper cores. CaIImediates this process by reversible binding at the Cu2O2core, highlighting the unique capability for metal‐ion binding events to stabilize novel reactive fragments and control O2activation in biomimetic systems. -
Calcium‐Ion Binding Mediates the Reversible Interconversion of Cis and Trans Peroxido Dicopper Coresmore » « less
Abstract Coupled dinuclear copper oxygen cores (Cu2O2) featured in type III copper proteins (hemocyanin, tyrosinase, catechol oxidase) are vital for O2transport and substrate oxidation in many organisms.
μ ‐1,2‐cis peroxido dicopper cores (C P ) have been proposed as key structures in the early stages of O2binding in these proteins; their reversible isomerization to other Cu2O2cores are directly relevant to enzyme function. Despite the relevance of such species to type III copper proteins and the broader interest in the properties and reactivity of bimetallicC P cores in biological and synthetic systems, the properties and reactivity ofC P Cu2O2species remain largely unexplored. Herein, we report the reversible interconversion ofμ ‐1,2‐trans peroxido (T P ) andC P dicopper cores. CaIImediates this process by reversible binding at the Cu2O2core, highlighting the unique capability for metal‐ion binding events to stabilize novel reactive fragments and control O2activation in biomimetic systems. -
more » « less
Abstract Although many monometallic active sites have been installed in metal–organic frameworks (MOFs) for catalytic reactions, there are no effective strategies to generate bimetallic catalysts in MOFs. Here we report the synthesis of a robust, efficient, and reusable MOF catalyst, MOF‐NiH, by adaptively generating and stabilizing dinickel active sites using the bipyridine groups in MOF‐253 with the formula of Al(OH)(2,2′‐bipyridine‐5,5′‐dicarboxylate) for
Z ‐selective semihydrogenation of alkynes and selective hydrogenation of C=C bonds in α,β‐unsaturated aldehydes and ketones. Spectroscopic studies established the dinickel complex (bpy⋅−)NiII(μ 2‐H)2NiII(bpy⋅−) as the active catalyst. MOF‐NiH efficiently catalyzed selective hydrogenation reactions with turnover numbers of up to 192 and could be used in five cycles of hydrogenation reactions without catalyst leaching or significant decrease of catalytic activities. The present work uncovers a synthetic strategy toward solution‐inaccessible Earth‐abundant bimetallic MOF catalysts for sustainable catalysis. -
more » « less
Abstract Although many monometallic active sites have been installed in metal–organic frameworks (MOFs) for catalytic reactions, there are no effective strategies to generate bimetallic catalysts in MOFs. Here we report the synthesis of a robust, efficient, and reusable MOF catalyst, MOF‐NiH, by adaptively generating and stabilizing dinickel active sites using the bipyridine groups in MOF‐253 with the formula of Al(OH)(2,2′‐bipyridine‐5,5′‐dicarboxylate) for
Z ‐selective semihydrogenation of alkynes and selective hydrogenation of C=C bonds in α,β‐unsaturated aldehydes and ketones. Spectroscopic studies established the dinickel complex (bpy⋅−)NiII(μ 2‐H)2NiII(bpy⋅−) as the active catalyst. MOF‐NiH efficiently catalyzed selective hydrogenation reactions with turnover numbers of up to 192 and could be used in five cycles of hydrogenation reactions without catalyst leaching or significant decrease of catalytic activities. The present work uncovers a synthetic strategy toward solution‐inaccessible Earth‐abundant bimetallic MOF catalysts for sustainable catalysis.
