Reduction of a Cerium(III) Siloxide Complex To Afford a Quadruple‐Decker Arene‐Bridged Cerium(II) Sandwich

Kelly, Robert L.; Maron, Laurent; Scopelliti, Rosario; Mazzanti, Marinella

doi:10.1002/ange.201709769

Cited by 12 publications

(4 citation statements)

References 66 publications

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“…Specifically, the first crystallographically‐characterizable examples of Y II , La II , Ce II , Pr II , Gd II , Tb II , Ho II , Er II , Lu II , Th II , U II , Np II , and Pu II have been isolated from reductions of tris(silylcyclopentadienyl) complexes as shown in Equation . Additionally, examples of these new ions in other ligand environments have also been reported …”

Section: Figurementioning

confidence: 96%

Evaluating Electron‐Transfer Reactivity of Complexes of Actinides in +2 and +3 Oxidation States by using EPR Spectroscopy

Moehring

Evans

2020

Chemistry A European J

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The possibility that the relative reactivity of complexes of actinidem etalsi nt he + 2a nd + 3o xidation states could be investigated by examining reactions between An III and An II species of Th and Uw ithr are-earth metal reagents that provide EPR confirmation of electron transfer reactivity has been explored. 2 ). 1À ,r espectively, which wereidentified by EPR spectroscopy.The reverse reactions also occur which indicates that the reduction potentials are similar.[ Cp'' 3 La II ] 1À reduces Cp' 3 Y III and the reverse Y II /La III combination also occurs.I nb othc ases, the reactions generate EPR spectra indicative of multiple species in the mixtures of La II and Y II ,w hich is consistent with ligand exchange and demonstrates that numeroush eteroleptic complexes of these Ln II ions exist.Ar ecent development in rare-earth and actinide chemistry is the discovery that the + 2oxidation state is availableincrystallographically characterizable molecular speciesf or many more metals than was previously expected. Specifically, the first crystallographically-characterizable

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Section: Figurementioning

confidence: 96%

Evaluating Electron‐Transfer Reactivity of Complexes of Actinides in +2 and +3 Oxidation States by using EPR Spectroscopy

Moehring

Evans

2020

Chemistry A European J

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“…However, it was Mazzanti and co‐workers who isolated the first molecular Tb IV complex using the electron rich O‐donor tris( tert ‐butoxy)siloxide ligand, a strategy previously used to stabilize the Ce IV analogue [63b] . The complex was prepared via oxidation of the Tb III precursor [Tb III (OSi(O t Bu) 3 ) 4 K] ( 48 ) employing [N(C 6 H 4 Br) 3 ][SbCl 6 ] to give [Tb IV (OSi(O t Bu) 3 ) 4 ] ( 49 ) shown in Figure 12, with the oxidation occurring at significantly less positive potentials compared to the standard Tb IV /Tb III redox couple [82b] .…”

Section: Lanthanoid Complexes With Unusual Lanthanoid Oxidation Statesmentioning

confidence: 99%

Lanthanoid Complexes as Molecular Materials: The Redox Approach

Hay

Boskovic

2021

Chemistry A European J

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The development of molecular materials with novel functionality offers promise for technological innovation. Switchable molecules that incorporate redox‐active components are enticing candidate compounds due to their potential for electronic manipulation. Lanthanoid metals are most prevalent in their trivalent state and usually redox‐activity in lanthanoid complexes is restricted to the ligand. The unique electronic and physical properties of lanthanoid ions have been exploited for various applications, including in magnetic and luminescent materials as well as in catalysis. Lanthanoid complexes are also promising for applications reliant on switchability, where the physical properties can be modulated by varying the oxidation state of a coordinated ligand. Lanthanoid‐based redox activity is also possible, encompassing both divalent and tetravalent metal oxidation states. Thus, utilization of redox‐active lanthanoid metals offers an attractive opportunity to further expand the capabilities of molecular materials. This review surveys both ligand and lanthanoid centered redox‐activity in pre‐existing molecular systems, including tuning of lanthanoid magnetic and photophysical properties by modulating the redox states of coordinated ligands. Ultimately the combination of redox‐activity at both ligands and metal centers in the same molecule can afford novel electronic structures and physical properties, including multiconfigurational electronic states and valence tautomerism. Further targeted exploration of these features is clearly warranted, both to enhance understanding of the underlying fundamental chemistry, and for the generation of a potentially important new class of molecular material.

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“…Following the discovery of the (Cp″ 3 Ln) − and (Cp′ 3 Ln) − complexes, a variety of other ligand systems, such as C 5 Me 4 H (Cp tet ), C 5 H 4 Me (Cp Me ), C 5 H 4 CMe 3 (Cp t ), C 5 i Pr 5 , NR 2 (R = SiMe 3 ), , and [( Ad,Me ArO) 3 mes], − have been found to support 4f n 5d 1 Ln(II) ions . Even though the coordination chemistry of the new 4f n 5d 1 Ln(II) ions has been expanded, the factors affecting their successful synthesis and stability are still not clear.…”

Section: Introductionmentioning

confidence: 99%

Room-Temperature Stable Ln(II) Complexes Supported by 2,6-Diadamantyl Aryloxide Ligands

Anderson-Sanchez

Furche

et al. 2023

Inorg. Chem.

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The sterically bulky aryloxide ligand OAr* (OAr* = –OC6H2-Ad2-2,6tBu-4; Ad = 1-adamantyl) has been used to generate Ln(II) complexes across the lanthanide series that are more thermally stable than complexes of any other ligand system reported to date for 4f n d1 Ln(II) ions. The Ln(III) precursors Ln(OAr*)3 (1-Ln) were synthesized by reacting 1.2 equiv of Ln(NR2)3 (R = SiMe3) with 3 equiv of HOAr* for Ln = La, Ce, Nd, Gd, Dy, Yb, and Lu. 1-Ce, 1-Nd, 1-Gd, 1-Dy, and 1-Lu were identified by single-crystal X-ray diffraction studies. Reductions of 1-Ln with potassium graphite (KC8) in tetrahydrofuran in the presence of 2.2.2-cryptand (crypt) yielded the Ln(II) complexes [K(crypt)][Ln(OAr*)3] (2-Ln). The 2-Ln complexes for Ln = Nd, Gd, Dy, and Lu were characterized by X-ray crystallography and found to have Ln–O bond distances 0.038–0.087 Å longer than those of their 1-Ln analogues; this is consistent with 4f n 5d1 electron configurations. The structure of 2-Yb has Yb–O distances 0.167 Å longer than those predicted for 1-Yb, which is consistent with a 4f14 electron configuration. Although 2-La and 2-Ce proved to be challenging to isolate, with 18-crown-6 (18-c-6) as the potassium chelator, La(II) and Ce(II) complexes with OAr* could be isolated and crystallographically characterized: [K(18-c-6)][Ln(OAr*)3] (3-Ln). The Ln(II) complexes decompose at room temperature more slowly than other previously reported 4f n 5d1 Ln(II) complexes. For example, only 30% decomposition of 2-Dy was observed after 30 h at room temperature compared to complete decomposition of [Dy(OAr′)3]− and [DyCp′3]− under similar conditions (OAr′ = OC6H2-2,6-tBu2-4-Me; Cp′ = C5H4SiMe3).

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Reduction of a Cerium(III) Siloxide Complex To Afford a Quadruple‐Decker Arene‐Bridged Cerium(II) Sandwich

Cited by 12 publications

References 66 publications

Evaluating Electron‐Transfer Reactivity of Complexes of Actinides in +2 and +3 Oxidation States by using EPR Spectroscopy

Evaluating Electron‐Transfer Reactivity of Complexes of Actinides in +2 and +3 Oxidation States by using EPR Spectroscopy

Lanthanoid Complexes as Molecular Materials: The Redox Approach

Room-Temperature Stable Ln(II) Complexes Supported by 2,6-Diadamantyl Aryloxide Ligands

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