Abstract:We report the small‐scale synthesis, isolated yield, single ‐crystal X‐ray structure, 1H NMR solution spectroscopy /solid‐state UV/Vis‐nIR spectroscopy, and density functional theory (DFT)/ab initio wave function theory calculations on an Am3+ organometallic complex, [Am(C5Me4H)3] (1). This constitutes the first quantitative data on Am−C bonding in a molecular species.
“…The average 1 - Nd M−Cent is larger than the reported M−Cent distance for Cp′ 3 Nd of 2.4885(3) Å 36 . The average metal centroid distance of 1 - Am , 2.524 Å, slightly varies with the literature value of 2.5174 Å for Cp tet 3 Am, likely due to steric effects of using Cp′ over Cp tet and an extra coordination site from 4,4′-bpy 17 . Fig.…”
Section: Resultsmentioning
confidence: 54%
“…The synthesis of Cp′ 3 Am was achieved by means of established synthetic methods for the dehydration of actinides using Me 3 Si−Br followed by the salt metathesis reaction with KCp′ to form a putative Cp′ 3 Am residue 17 , 20 , 38 . Modeled on the structure of Mehdoui’s (Cp′ 3 U) 2 ( μ -4,4′-bpy), the addition of 4,4′-bpy to Cp′ 3 M in toluene results in an immediate precipitate 39 .…”
Section: Resultsmentioning
confidence: 99%
“…Alternatively, actinide−carbon bonding, particularly in transplutonium elements, is exceedingly under-characterized considering the impact that organoactinide chemistry has built on understanding bonding within the f -block 17 , 18 . Historically, cyclopentadienide (Cp − = C 5 H 5 ) was used to synthesize the first transuranic organometallic complexes, and its derivatives, Cp tet (C 5 Me 4 H), Cp′ (C 5 H 4 SiMe 3 ), and Cp′′ [C 5 H 3 (SiMe 3 ) 2 ] have paved the way for solving the unusual bonding and redox chemistry observed in these elements 17 , 19 – 36 . Recent advances in transuranic synthesis have yielded the structural characterization of organometallic plutonium and americium complexes 17 , 19 , 20 .…”
Section: Introductionmentioning
confidence: 99%
“…Historically, cyclopentadienide (Cp − = C 5 H 5 ) was used to synthesize the first transuranic organometallic complexes, and its derivatives, Cp tet (C 5 Me 4 H), Cp′ (C 5 H 4 SiMe 3 ), and Cp′′ [C 5 H 3 (SiMe 3 ) 2 ] have paved the way for solving the unusual bonding and redox chemistry observed in these elements 17 , 19 – 36 . Recent advances in transuranic synthesis have yielded the structural characterization of organometallic plutonium and americium complexes 17 , 19 , 20 . Single-crystal characterization of an organoamericium complex, [(C 5 Me 4 H) 3 Am], was obtained in 2019, and there is no published organometallic single-crystal characterization for elements heavier than americium to date 17 .…”
Section: Introductionmentioning
confidence: 99%
“…Recent advances in transuranic synthesis have yielded the structural characterization of organometallic plutonium and americium complexes 17 , 19 , 20 . Single-crystal characterization of an organoamericium complex, [(C 5 Me 4 H) 3 Am], was obtained in 2019, and there is no published organometallic single-crystal characterization for elements heavier than americium to date 17 . However, Cp′ has not yet been applied to americium chemistry due to its formation of highly soluble products in common glovebox solvents, leading to difficult crystallization.…”
Variations in bonding between trivalent lanthanides and actinides is critical for reprocessing spent nuclear fuel. The ability to tune bonding and the coordination environment in these trivalent systems is a key factor in identifying a solution for separating lanthanides and actinides. Coordination of 4,4′−bipyridine (4,4′−bpy) and trimethylsilylcyclopentadienide (Cp′) to americium introduces unexpectedly ionic Am−N bonding character and unique spectroscopic properties. Here we report the structural characterization of (Cp′3Am)2(μ − 4,4′−bpy) and its lanthanide analogue, (Cp′3Nd)2(μ − 4,4′−bpy), by single-crystal X-ray diffraction. Spectroscopic techniques in both solid and solution phase are performed in conjunction with theoretical calculations to probe the effects the unique coordination environment has on the electronic structure.
“…The average 1 - Nd M−Cent is larger than the reported M−Cent distance for Cp′ 3 Nd of 2.4885(3) Å 36 . The average metal centroid distance of 1 - Am , 2.524 Å, slightly varies with the literature value of 2.5174 Å for Cp tet 3 Am, likely due to steric effects of using Cp′ over Cp tet and an extra coordination site from 4,4′-bpy 17 . Fig.…”
Section: Resultsmentioning
confidence: 54%
“…The synthesis of Cp′ 3 Am was achieved by means of established synthetic methods for the dehydration of actinides using Me 3 Si−Br followed by the salt metathesis reaction with KCp′ to form a putative Cp′ 3 Am residue 17 , 20 , 38 . Modeled on the structure of Mehdoui’s (Cp′ 3 U) 2 ( μ -4,4′-bpy), the addition of 4,4′-bpy to Cp′ 3 M in toluene results in an immediate precipitate 39 .…”
Section: Resultsmentioning
confidence: 99%
“…Alternatively, actinide−carbon bonding, particularly in transplutonium elements, is exceedingly under-characterized considering the impact that organoactinide chemistry has built on understanding bonding within the f -block 17 , 18 . Historically, cyclopentadienide (Cp − = C 5 H 5 ) was used to synthesize the first transuranic organometallic complexes, and its derivatives, Cp tet (C 5 Me 4 H), Cp′ (C 5 H 4 SiMe 3 ), and Cp′′ [C 5 H 3 (SiMe 3 ) 2 ] have paved the way for solving the unusual bonding and redox chemistry observed in these elements 17 , 19 – 36 . Recent advances in transuranic synthesis have yielded the structural characterization of organometallic plutonium and americium complexes 17 , 19 , 20 .…”
Section: Introductionmentioning
confidence: 99%
“…Historically, cyclopentadienide (Cp − = C 5 H 5 ) was used to synthesize the first transuranic organometallic complexes, and its derivatives, Cp tet (C 5 Me 4 H), Cp′ (C 5 H 4 SiMe 3 ), and Cp′′ [C 5 H 3 (SiMe 3 ) 2 ] have paved the way for solving the unusual bonding and redox chemistry observed in these elements 17 , 19 – 36 . Recent advances in transuranic synthesis have yielded the structural characterization of organometallic plutonium and americium complexes 17 , 19 , 20 . Single-crystal characterization of an organoamericium complex, [(C 5 Me 4 H) 3 Am], was obtained in 2019, and there is no published organometallic single-crystal characterization for elements heavier than americium to date 17 .…”
Section: Introductionmentioning
confidence: 99%
“…Recent advances in transuranic synthesis have yielded the structural characterization of organometallic plutonium and americium complexes 17 , 19 , 20 . Single-crystal characterization of an organoamericium complex, [(C 5 Me 4 H) 3 Am], was obtained in 2019, and there is no published organometallic single-crystal characterization for elements heavier than americium to date 17 . However, Cp′ has not yet been applied to americium chemistry due to its formation of highly soluble products in common glovebox solvents, leading to difficult crystallization.…”
Variations in bonding between trivalent lanthanides and actinides is critical for reprocessing spent nuclear fuel. The ability to tune bonding and the coordination environment in these trivalent systems is a key factor in identifying a solution for separating lanthanides and actinides. Coordination of 4,4′−bipyridine (4,4′−bpy) and trimethylsilylcyclopentadienide (Cp′) to americium introduces unexpectedly ionic Am−N bonding character and unique spectroscopic properties. Here we report the structural characterization of (Cp′3Am)2(μ − 4,4′−bpy) and its lanthanide analogue, (Cp′3Nd)2(μ − 4,4′−bpy), by single-crystal X-ray diffraction. Spectroscopic techniques in both solid and solution phase are performed in conjunction with theoretical calculations to probe the effects the unique coordination environment has on the electronic structure.
This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.
The synthesis,s tructure,a nd spectroscopic characterization of the first transplutonium metal-organic framework (MOF) is described. The preparation and structure of Am-GWMOF-6, [Am 2 (C 6 H 8 O 4 ) 3 (H 2 O) 2 ][(C 10 H 8 N 2 )],i sa nalogous to that of the isostructural trivalent lanthanide-only containing material GWMOF-6. The presented MOF architecture is used as ap latform to probe Am 3+ coordination chemistry and guest-enhanced luminescent emission, whereas the framework itself provides ameans to monitor the effects of self-irradiation upon crystallinity over time.P resented here is ad iscussion of these properties and the opportunities that MOFs providei nt he structural and spectroscopic study of actinides.
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