2023
DOI: 10.1021/acs.inorgchem.3c00455
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Evaluating f-Orbital Participation in the UV═E Multiple Bonds of [U(E)(NR2)3] (E = O, NSiMe3, NAd; R = SiMe3)

Abstract: The reaction of 1 equiv of 1-azidoadamantane with [U III (NR 2 ) 3 ] (R = SiMe 3 ) in Et 2 O results in the formation of [U V (NR 2 ) 3 (NAd)] (1, Ad = 1-adamantyl) in good yields. The electronic structure of 1, as well as those of the related U(V) complexes, [U V (NR 2 ) 3 (NSiMe 3 )] (2) and [U V (NR 2 ) 3 (O)] (3), were analyzed with EPR spectroscopy, SQUID magnetometry, NIR−visible spectroscopy, and crystal field modeling. This analysis revealed that, within this series of complexes, the steric bulk of the… Show more

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Cited by 10 publications
(20 citation statements)
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“…2–4 This blends in not only with the interest of small-molecule activation using organoactinide complexes in general, 5 but also the more fundamental question of how to describe their bonding, more specifically the degree of covalence and the impact of the 6d and 5f orbitals. 6 For many years, we have focused on the synthesis and reactivity of thorium and uranium complexes containing metal–ligand multiple bonds, 7 where our most recent contribution represents the Lewis base-supported uranium terminal imido metallocene [η 5 -1,2,4-(Me 3 Si) 3 C 5 H 2 ] 2 UN( p -tolyl)(dmap) ( 1 ), 8 which is a useful precursor for the synthesis of the terminal oxido, sulfido and selenido uranium metallocenes [η 5 -1,2,4-(Me 3 Si) 3 C 5 H 2 ] 2 UE (E = O, S, Se) by cycloaddition–elimination reactions with Ph 2 CE (E = O, S) or ( p -MeOPh) 2 CSe. 8 Encouraged by this, we have now extended these studies to other small molecules.…”
Section: Introductionmentioning
confidence: 99%
“…2–4 This blends in not only with the interest of small-molecule activation using organoactinide complexes in general, 5 but also the more fundamental question of how to describe their bonding, more specifically the degree of covalence and the impact of the 6d and 5f orbitals. 6 For many years, we have focused on the synthesis and reactivity of thorium and uranium complexes containing metal–ligand multiple bonds, 7 where our most recent contribution represents the Lewis base-supported uranium terminal imido metallocene [η 5 -1,2,4-(Me 3 Si) 3 C 5 H 2 ] 2 UN( p -tolyl)(dmap) ( 1 ), 8 which is a useful precursor for the synthesis of the terminal oxido, sulfido and selenido uranium metallocenes [η 5 -1,2,4-(Me 3 Si) 3 C 5 H 2 ] 2 UE (E = O, S, Se) by cycloaddition–elimination reactions with Ph 2 CE (E = O, S) or ( p -MeOPh) 2 CSe. 8 Encouraged by this, we have now extended these studies to other small molecules.…”
Section: Introductionmentioning
confidence: 99%
“…Indeed, the largest component of all states is the one predicted from the zeroth order except for the doublet at 7525 cm −1 , which is composed by similar amounts of |2,+1/2⟩ and |3,−1/2⟩. It is noticeable that the calculated extent of mixing of states in 4 appears to be significantly more than that reported for [U(NR){N(SiMe 3 ) 2 } 3 ] (R = Ad, SiMe 3 ), 85 which we suggest stems from a larger crystal field for 4 resulting in more mixing overall. Hence, it would seem that the NBO Dipp ligand brings more crystal field splitting than the bis(trimethylsilyl)amide, consistent with their O vs N donor natures.…”
Section: ■ Results and Discussionmentioning
confidence: 63%
“…Certainly, the absorption at ∼17 500 cm −1 is very broad, likely from unresolved vibronic coupling�recall the U�NAd group stretching frequencies of ∼970 and ∼650 cm −1 �and that this absorption is a shoulder on the side of a more intense feature. That this feature is so intense likely stems from intensity stealing (5f σ and N sp orbital mixing) 98 85 The absorptions in the approximate range 7042−9328 cm −1 also appear to exhibit vibronic coupling, though this is not obviously resolved, but we note that the approximate separations of the three lowest lying absorptions are similar to the most energetic U−NAd stretching mode. Assuming that the peaks at ∼7042 and ∼7267 cm −1 are a split feature and likewise for the absorptions at ∼8666 and ∼9328 cm −1 , then they are averaged (to 7155 and 8997 cm −1 , respectively).…”
Section: ■ Results and Discussionmentioning
confidence: 74%
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