Silyl‐Phosphino‐Carbene Complexes of Uranium(IV)

Lu, Erli; Boronski, Josef T.; Gregson, Matthew; Wooles, Ashley J.; Liddle, Stephen T.

doi:10.1002/ange.201802080

Cited by 15 publications

(15 citation statements)

References 92 publications

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“…In 2018, they also presented the "mixed" bis carbene complexes with 6a and the formal coordinated dianion (C(SiMe 3 )(PPh 2 )). 105 The latter dianion cannot be synthesized as a free geminal dianion, the fragment was constructed in the coordination sphere of the U-carbene complex. It relied on the coordination of the corresponding anion and deprotonation by the carefully optimized basic CHPh(SiMe 3 ) ligand.…”

Section: Scheme 36: Reactivity Of Y Carbene Complexes With Carbonyl Derivatives: Ketones Andmentioning

confidence: 99%

“…In 2018, Liddle provided the first example of divergent carbene and phosphine reactivities with their bis carbene U(IV) complexes. 105 With aldehydes, the classical Wittig type chemistry of the U=C bond was observed to form the two expected alkene derivatives (in an unselective manner), whereas the reaction with diphenyl-acetylene yields a complex featuring a metalacycle in which the U=C carb moiety is intact (scheme 47).…”

Section: Reactivity Of Actinide Complexesmentioning

confidence: 99%

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Geminal Dianions Stabilized by Main Group Elements

2019

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This review is dedicated to the chemistry of stable and isolable species that bear two lone pairs at the same C center, i.e. geminal dianions, stabilized by main group elements. Three cases can thus be considered: the gem dilithio derivative, for which the two substituents at C are neutral, the ylidiide derivatives, for which one substituent is neutral while the other is charged, and finally the geminal bisylides, for which the two substituents are positively charged. In this review the syntheses and electronic structures of the geminal dianions are presented, followed by the studies dedicated to their reactivity toward organic substrates and finally to their coordination chemistry and applications. Reactivity of doubleylides towards organic compounds. 4.4. Coordination chemistry of double ylides to metallic species. 4.4.1. Coordination to Group 2 Metals. 4.4.2. Coordination to Actinides: Uranium Complexes 4.4.3. Coordination to Group 4 Metals: Zirconium Complexes 4.4.4. Coordination to Group 6 Metals: Tungsten Complexes 4.4.5. Coordination to Group 7 Metals: Manganese and Rhenium Complexes 4.4.6. Coordination to Group 8 Metals: Iron Complexes 4.4.7. Coordination to Group 9 Metals: Rhodium and Iridium Complexes 4.4.8. Coordination to Group 10 Metals 4.4.9. Coordination to Group 11 (Coinage) Metals 4.4.10. Coordination to Group 12 Metals 4.5. Reactivity of double ylides towards main group elements. 4.5.1. Group 13 4.5.2. Group 14 4.5.3. Group 15 4.5.4. Group 16 4.5.5. Group 17 4.6. Carbodicarbenes 4.6.1. Synthesis 4.6.2. Reactivity 4.6.3. Coordination chemistry 4.6.4. Reactivity with main group elements 5. Conclusion 6. Acknowledgements 7. References lengths in complexes [(7)Mg(THF)] 2 and [(14)Mg(THF) 3 ] at 2.156(5)Å and 2.113(4)Å resp. are as expectedly significantly shorter than the ones measured in the dimers [(6a)Mg] 2 and [(10)Mg] 2 at 2.225(2)Å (av.) and 2.267(3)Å (av.). Electronic structureThe question of the nature of the bond between the AE metal and C was addressed. Harder et al.performed a DFT study first on models of [(6a)Ca] 2 and [(6f)Ca] where H atoms were considered in place of the real phenyl groups at P and groups (SiMe 3 and Ar resp.) at N. 49 In the case of the monomeric complex [(6f)Ca], the solvent molecules were not taken into account. Not surprising in light of the difference of electronegativity of the elements, the charge at C varied between -1.623 (monomer) and -1.847 (dimer) whereas charge at Ca varied between +1.760 (monomer) and +1.821 (dimer). The Ca-C bond was thus described as highly ionic. The calculations with the full dimeric system were carried out, and a slightly reduced charge was calculated at C (-1.778). The NPA charges were also compared to the ones in neutral 6aH 2 and the [Ca(6aH) 2 ] complex. Expectedly the charge at C goes from -1.079 to -1.409 to -1.778 (in 6aH2, [Ca(6aH) 2 ], [Ca(6a)] 2 resp.). The charge at N also increases (-1.474 to -1.580 to -1.665 resp.) upon deprotonation at C. Conversely, the charge at P varies but to a small extent (+1.747 to +1.727 to +1.7...

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Section: Scheme 36: Reactivity Of Y Carbene Complexes With Carbonyl Derivatives: Ketones Andmentioning

confidence: 99%

Section: Reactivity Of Actinide Complexesmentioning

confidence: 99%

Geminal Dianions Stabilized by Main Group Elements

2019

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“…Thus, the question arises as to whether the electronic structures of actinide complexes can be substantially altered through the design of specific electronic attributes of the ligands surrounding it given the complexities of the metal ions in these systems. While there are certainly numerous examples of the use of ligands to create specific symmetries 29 , 30 , large binding constants 31 , 32 , and open-coordination sites around actinides that lead to unique reactivities 12 , 33 – 39 , substantial changes in bonding might also be achievable in actinide complexes by using ligands that create large dipole moments. Guidance on how to achieve this effect exists from the large body of work for designing organic nonlinear optical materials 40 .…”

Section: Introductionmentioning

confidence: 99%

Creation of an unexpected plane of enhanced covalency in cerium(III) and berkelium(III) terpyridyl complexes

et al. 2021

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Controlling the properties of heavy element complexes, such as those containing berkelium, is challenging because relativistic effects, spin-orbit and ligand-field splitting, and complex metal-ligand bonding, all dictate the final electronic states of the molecules. While the first two of these are currently beyond experimental control, covalent M‒L interactions could theoretically be boosted through the employment of chelators with large polarizabilities that substantially shift the electron density in the molecules. This theory is tested by ligating BkIII with 4’-(4-nitrophenyl)-2,2’:6’,2”-terpyridine (terpy*), a ligand with a large dipole. The resultant complex, Bk(terpy*)(NO3)3(H2O)·THF, is benchmarked with its closest electrochemical analog, Ce(terpy*)(NO3)3(H2O)·THF. Here, we show that enhanced Bk‒N interactions with terpy* are observed as predicted. Unexpectedly, induced polarization by terpy* also creates a plane in the molecules wherein the M‒L bonds trans to terpy* are shorter than anticipated. Moreover, these molecules are highly anisotropic and rhombic EPR spectra for the CeIII complex are reported.

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“…3 Dy] 2 (Cp t = C 5 H 4 CMe 3 ), 17 [K(crypt)][Cp Me 3 Dy] (Cp Me = C 5 H 4 Me), 18 [K(crypt)][Sc(OAr′) 3 ] (OAr′ = OC 6 H 2 -t-Bu 2 -2,6-Me-4), 19 [K (crypt)][(( Ad,Me ArO) 3 mes)Ln] (Ln = Nd, Gd, Dy, Er; ( Ad,Me ArO) 3 20 [Rb (crypt)][Ln(NR 2 ) 3 ] (Ln = Nd, Ho, Er), 21 and [Cs(crypt)][Sc(NR 2 ) 3 ] (R = SiMe 3 ). 22 Additionally, the crypt ligand in [Li(crypt)] 1+ countercations has also been found as crypt-κ 6 in three different binding modes: N 2 O 4 , 14,23 NO 5 , 14,[23][24][25][26][27][28][29] and O 6 . 14 However, the crypt ligand can also encapsulate rare-earth metals ions as well as alkali metal ions.…”

Section: Introductionmentioning

confidence: 99%