Synthesis of Uranium–Ligand Multiple Bonds by Cleavage of a Trityl Protecting Group

Smiles, Danil E.; Wu, Guang; Hayton, Trevor W.

doi:10.1021/ja411423a

Cited by 73 publications

(90 citation statements)

References 46 publications

(62 reference statements)

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“…The single other reported crystal structure of this type was published by Thomas and co‐workers in their studies of Co/Zr heterobimetallic catalytic hydrosilylation, [N 2 Co(MesNP i Pr 2 ) 3 Zr(OCPhPh‐CPh 2 O)Zr(MesNP i Pr 2 ) 3 CoN 2 ], which had the shortest coupled C−C bond length at 1.496(5) Å . Compared with the reported U IV (OCPh 3 )[N(SiMe 3 ) 2 ] 3 , which had a U−O bond length of 2.098(3) Å, compound 1.2 had similar U−O bond lengths, averaging 2.102(5) Å . Additionally, the average U−N amide bonds were comparable with bond lengths of 2.281(4) and 2.284(6) Å for U IV (OCPh 3 )[N(SiMe 3 ) 2 ] 3 and 1.2 respectively.…”

Section: Resultscontrasting

confidence: 84%

“…Synthesis of Tp* 2 U IV O was accomplished by O‐atom transfer from pyridine‐ N ‐oxide and TEMPO to Tp* 2 U III (2,2′‐bpy) and Tp* 2 U III (OC⋅Ph 2 ), respectively . The Hayton group has synthesized a capped uranium(IV) oxo complex, [K(18‐crown‐6)][U IV O[N(SiMe 3 ) 2 ] 3 , by reductive deprotection of a trityl alkoxide complex, U IV (OCPh 3 )[N(SiMe 3 ) 2 ] 3 . This is a similar strategy to ours, though differentiated by our use of organic amides as oxo transfer reagents.…”

Section: Resultsmentioning

confidence: 73%

See 1 more Smart Citation

Reduction of Carbonyl Groups by Uranium(III) and Formation of a Stable Amide Radical Anion

Mullane

Cheisson

Nakamaru‐Ogiso

et al. 2017

Chemistry A European J

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Methyl benzoate, N,N-dimethylbenzamide, and benzophenone were reduced by U [N(SiMe ) ] resulting in uranium(IV) products. Reduction of benzophenone lead to U [OC⋅Ph )][N(SiMe ) ] , (1.1) which forms the dinuclear complex, [N(SiMe ) ] U (OCPhPh-CPh O)U [N(SiMe ) ] (1.2), through coupling of the ketyl radical species upon crystallization. Reaction of N,N-dimethylbenzamide with U [N(SiMe ) ] resulted in U [OC⋅(Ph)(NMe )][N(SiMe ) ] (2), a uranium(IV) compound and the first example of a charge-separated amide radical. In the case of methyl benzoate, the reduction resulted in U (OMe)[N(SiMe ) ] (3) and benzaldehyde as the reduced organic fragment. Compound 2 showed the ability to act as a uranium(III) synthon in its reactivity with trimethylsilyl azide, a reaction that yielded U (=NSiMe )[N(SiMe ) ] . Additionally, 2 was reduced with potassium graphite resulting in [U(μ-O)[O=C(NMe )(Ph)][N(SiMe ) ] ] (4), a dinuclear uranium compound bridged by oxo ligands. Reduction of 2 in the presence of 15-crown-5 afforded isolation of the mono-oxo compound, [(15-crown-5) K][UO[N(SiMe ) ] ] (5). The results expand the reduction capabilities of U complexes and demonstrate a strategy for isolating novel metal-stabilized radicals.

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Section: Resultscontrasting

confidence: 84%

Section: Resultsmentioning

confidence: 73%

Reduction of Carbonyl Groups by Uranium(III) and Formation of a Stable Amide Radical Anion

Mullane

Cheisson

Nakamaru‐Ogiso

et al. 2017

Chemistry A European J

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“…This desire stems not only from a need to develop our knowledge and understanding of actinide bonding at a fundamental level45678, but also because of potential applications in nuclear waste clean-up which might utilize extraction methods that exploit covalency differences in metal-ligand bonding9. Because actinide-ligand multiple bonds arguably contain the greatest opportunities to probe covalency101112, in recent years in addition to numerous oxo complexes12 there has been intensive progress in uranium-carbene13141516171819, -imido202122232425262728, -nitride29303132, -phosphinidene/-arsinidene/-arsenido33343536 and -chalcogenido (S, Se, Te) chemistry37383940. This work demonstrates the wide range of multiply bonded ligands that can be stabilised at uranium with appropriate supporting ligands, and also that softer, heavier main group element centres can be stabilised as well as relatively hard first-row elements such as C, N and O.…”

mentioning

confidence: 99%

Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions

et al. 2016

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Despite the burgeoning field of uranium-ligand multiple bonds, analogous complexes involving other actinides remain scarce. For thorium, under ambient conditions only a few multiple bonds to carbon, nitrogen, oxygen, sulfur, selenium and tellurium are reported, and no multiple bonds to phosphorus are known, reflecting a general paucity of synthetic methodologies and also problems associated with stabilising these linkages at the large thorium ion. Here we report structurally authenticated examples of a parent thorium(IV)–phosphanide (Th–PH2), a terminal thorium(IV)–phosphinidene (Th=PH), a parent dithorium(IV)–phosphinidiide (Th–P(H)-Th) and a discrete actinide–phosphido complex under ambient conditions (Th=P=Th). Although thorium is traditionally considered to have dominant 6d-orbital contributions to its bonding, contrasting to majority 5f-orbital character for uranium, computational analyses suggests that the bonding of thorium can be more nuanced, in terms of 5f- versus 6d-orbital composition and also significant involvement of the 7s-orbital and how this affects the balance of 5f- versus 6d-orbital bonding character.

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“…If the procedure was carried out without the mixed solvent conditions, we observed multiple paramagnetic species by 1 H NMR spectroscopy, which included small amounts of the bridging nitride complex [(Me 3 Si) 2 N ] 3 U V (N)U IV [N(SiMe 3 ) 2 ] 3 , the X‐ray structure of which is included in the Supporting Information (Figure S26). The formation of actinide ligand multiple bonds by trityl deprotection has been established by the Hayton group to yield [An IV (=S)[N(SiMe 3 ) 2 ] 3 ] − [An IV (=O)[N(SiMe 3 ) 2 ] 3 ] − (An=U, Th) complexes . It is feasible that [(Me 3 Si) 2 N ] 3 U V (N)U IV [N(SiMe 3 ) 2 ] 3 was produced from a similar reaction pathway.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Reduction of Uranium(V) Imido Complexes with Redox‐Active Substituents

Mullane

Carroll

Schelter

2017

Chemistry A European J

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Organic azides that contain naphthyl functional groups were used to prepare uranium(V) imido complexes U [=NC(2-naph)Ph ][N(SiMe ) ] (2), U [=NC(2-naph) ][N(SiMe ) ] (3), and U [=N(2-naph)][N(SiMe ) ] (4), and their properties were compared with U [=NCPh ][N(SiMe ) ] (1). The electronic structures of these compounds were investigated by solution electrochemistry studies, which revealed accessible U , U , and naphthalene /naphthalene couples. The uranium(V) naphthylimido complexes were reduced by potassium graphite to yield their uranium(IV) congeners K[U [=NC(2-naph)Ph ][N(SiMe ) ] ] (2-K), K[U [=NC(2-naph) ][N(SiMe ) ] ] (3-K), and K[U [=N(2-naph)][N(SiMe ) ] ] (4-K). The electronic structure of the dianionic compounds were investigated by DFT calculations, and this revealed that the second reduction was ligand-based, which opens the possibility of accomplishing multi-electron redox chemistry by using a tailored multiply-bonded ligand.

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Synthesis of Uranium–Ligand Multiple Bonds by Cleavage of a Trityl Protecting Group

Cited by 73 publications

References 46 publications

Reduction of Carbonyl Groups by Uranium(III) and Formation of a Stable Amide Radical Anion

Reduction of Carbonyl Groups by Uranium(III) and Formation of a Stable Amide Radical Anion

Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions

Synthesis and Reduction of Uranium(V) Imido Complexes with Redox‐Active Substituents

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