The Synthesis, Structures and Polymorphism of the Dimeric Trivalent Rare‐Earth 3,5‐Dimethylpyrazolate Complexes [Ln(Me2pz)3(thf)]2

Deacon, Glen B.; Harika, Rita; Junk, Peter Courtney; Skelton, Brian W.; Werner, Daniel; White, Allan H.

doi:10.1002/ejic.201400099

Cited by 17 publications

(17 citation statements)

References 63 publications

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“…The IR spectra show the Me 2 pz v̄ (CN) absorption at 1521‐1516 cm −1 for complexes 1 – 3 , 6 , and 7 , with an additional band at 1538 cm −1 in 2 b , corresponding to the Me 2 pzH ligand. Such spectroscopic features are consistent with other rare‐earth‐metal pyrazolate complexes . The UV/Vis spectra of all compounds as depicted in Figures S28–32 revealed molar absorptivities consistent with ligand to metal charge transfers in other Ce IV systems, e.g., homoleptic [Ce{N=C(NMe 2 ) 2 } 4 ] 2 (17 155 and 12 078 mol −1 cm −1 ), or [Ce{N(SiMe 3 ) 2 } 3 Cl] ( ϵ =2520 mol −1 cm −1 ), Notably, the mono‐solvated [Ce(Me 2 pz) 4 (thf)] ( 2 a ) complex exhibits a significantly larger molar absorptivity of 15 000 mol −1 cm −1 compared with [Ce(Me 2 pz) 4 ] 2 ( 1 , 7900 mol −1 cm −1 ).…”

Section: Resultssupporting

confidence: 79%

“…The formation of 3 supported our initial hypothesis that the [N(SiHMe 2 ) 2 ] moiety engages in the decomposition process, and the bpsa ligand formation involves Si−H bond activation. It should also be noted that when the diisopropylamide complex, [Ce(N i Pr 2 ) 4 ], was treated with four equivalents of Me 2 pzH in toluene, the reaction mixture changed color to light red within seconds of Me 2 pzH addition, and crystallization from n ‐hexane gave only crystals of the previously reported trivalent complex [Ce(Me 2 pz) 3 (Me 2 pzH)] 2 , in moderate yield (34 %).…”

Section: Resultsmentioning

confidence: 94%

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Emergence of a New [NNN] Pincer Ligand via Si−H Bond Activation and β‐Hydride Abstraction at Tetravalent Cerium

Werner

Bayer

Schädle

et al. 2020

Chemistry A European J

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The cerium(IV) pyrazolate complexes [Ce(Me2pz)4]2 and [Ce(Me2pz)4(thf)] initiate β‐hydride abstraction of the bis(dimethylsilyl)amido moiety, to afford a heteroleptic cerium(IV) species containing a dimethylpyrazolyl‐substituted silylamido ligand, namely [Ce(Me2pz)3(bpsa)] (bpsa=bis((3,5‐dimethylpyrazol‐1‐yl)dimethylsilyl)amido; Me2pz =3,5‐dimethylpyrazolato), along with some cerium(III) species. Remarkably, the nucleophilic attack of the pyrazolyl at the silicon atom and concomitant Si−H‐bond cleavage is restricted to the tetravalent cerium oxidation state and appears to proceed via the formation of a transient cerium(IV) hydride, which engages in immediate redox chemistry. When [Ce(Me2pz)4]2 is treated with [Li{N(SiMe3)2}], that is, in the absence of the SiH functionality, any redox chemistry did not occur. Instead, the ceric ate complex [LiCe2(Me2pz)9] and the stable mixed‐ligand ceric species [Ce(Me2pz)2{N(SiMe3)2}2] were obtained.

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Section: Resultssupporting

confidence: 79%

Section: Resultsmentioning

confidence: 94%

Emergence of a New [NNN] Pincer Ligand via Si−H Bond Activation and β‐Hydride Abstraction at Tetravalent Cerium

Werner

Bayer

Schädle

et al. 2020

Chemistry A European J

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“…To further determine the capacity of Ce IV in ketone conversion, and whether such equilibria are restricted to the tetravalent oxidation state, we compared the activation ability of the corresponding trivalent pyrazolate complex species toward bp. Accordingly, [Ln(Me 2 pz) 3 (thf)] [Ln = La ( 6a ), Lu ( 6b )] and [Ce(Me 2 pz) 3 ] ( 7 ) were treated with bp (3 equiv. for Ce; 2 equiv.…”

Section: Resultsmentioning

confidence: 99%

“…CeCl 3 was purchased from Sigma–Aldrich and converted into CeCl 3 (thf) 1.05 through Soxhlet extraction. Compounds [Ce(Me 2 pz) 4 ] 2 ( 1 ), [Ce(Me 2 pz) 3 ] ( 7 ), and [Ln(Me 2 pz) 3 (thf)] 2 [Ln = La ( 6a ), Lu ( 6b )] were synthesized according to published procedures , . The NMR spectra of air‐ and moisture‐sensitive compounds were performed in predried (with NaK) [D 6 ]benzene (C 6 D 6 ), [D 8 ]toluene, or [D 8 ]THF with J.…”

Section: Methodsmentioning

confidence: 99%

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Facile Reversible Benzophenone Insertion into Rare‐Earth Metal Pyrazolate Complexes

et al. 2017

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Treatment of the homoleptic Ce IV pyrazolate complex [Ce(Me 2 pz) 4 ] 2 (Me 2 pz = 3,5-dimethylpyrazolato) with benzophenone (bp) led to the formation of an Me 2 pz-substituted diphenylmethoxy-(N,O)-chelating ligand (pdpm), possibly metal-templated through initial coordination of bp to the cerium atom and subsequent bp insertion into the Ce-N(Me 2 pz) bond. This coordination/insertion process was shown to be reversible, leading to a complex sequence of equilibria involving multiple degrees of insertion/de-insertion and association/dissociation. The dependency on temperature and the amount of bp of all equilibria was revealed, with insertion/association of bp being favored at low temperatures and de-insertion/dissociation preferentially occurring at elevated temperatures. Such [a]

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Synthesis and Structures of Oxide ‐Centred Alkali Metal (K, Li)/Lanthanoid (Ln3 or 4) 3,5‐Dimethylpyrazolate Cages ‐ Herbert Schumann Revisited

Werner,

Guo,

Deacon

et al. 2024

Chemistry An Asian Journal

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Reaction of lanthanoid tris(3,5‐dimethylpyrazolate) compounds, [Ln(Me2pz)3(thf)]2 (Ln = La 1a, Ce, Pr, Dy 1b, Yb, Lu) with potassium or lithium bistrimethylsilylamide and with or without added 3,5‐dimethylpyrazole, or of lanthanoid tris(bistrimethylsilyl)amide complexes with potassium bistrimethylsilylamide and 3,5‐dimethylpyrazole have yielded a variety of oxide centred Ln3 or Ln4/(K or Li)1‐3 multinuclear cages, namely, [La4O(Me2pz)11K(thf)2] (2a), [La4O(Me2pz)11Li(Me2pzH)]⋅0.5Hexane (2b), [La4O(Me2pz)10(Me2pzH)] (2c) (from heating 1a in toluene), [Ce3O(Me2pz)9K2(dme)2] (3a), [Ce3O(Me2pz)9Li2(thf)2]⋅0.5Hexane (3b) and [Ce(Me2pz)5Li2(thf)3] (3c), which crystallized together, [Ce3O(Me2pz)10K3(thf)3] (3d), [Pr3O(Me2pz)10K3(thf)3] (4), [Dy3O(Me2pz)9K2(thf)2]·THF (5), [Yb3O(Me2pz)9K2(thf)2]·THF (6), and [Lu3O(Me2pz)9K2(thf)2]⋅THF (7). Crystals of {[K8(Me2pz)8(thf)2]⋅THF}∞ (8) were also obtained from the preparation of 7. From reaction of [Ce(Me2pz)3(thf)]2 with potassium tert‐butoxide in toluene, the cerium(IV) heterobimetallic polymer [Ce2(Me2pz)6(OtBu)4K2]∞ (9) was isolated. In the Ln3O and the Ln4O cages, the Ln atoms have triangular and distorted tetrahedral arrangements about the central oxygen, respectively. All metals are bound to the cages by a variety of pyrazolate binding modes, with up to five different exhibited in some structures, and a new coordination mode, μ4‐1κ(N):2κ(N′):η5:η5, was observed in two complexes.

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The Synthesis, Structures and Polymorphism of the Dimeric Trivalent Rare‐Earth 3,5‐Dimethylpyrazolate Complexes [Ln(Me₂pz)₃(thf)]₂

Cited by 17 publications

References 63 publications

Emergence of a New [NNN] Pincer Ligand via Si−H Bond Activation and β‐Hydride Abstraction at Tetravalent Cerium

Emergence of a New [NNN] Pincer Ligand via Si−H Bond Activation and β‐Hydride Abstraction at Tetravalent Cerium

Facile Reversible Benzophenone Insertion into Rare‐Earth Metal Pyrazolate Complexes

Synthesis and Structures of Oxide ‐Centred Alkali Metal (K, Li)/Lanthanoid (Ln3 or 4) 3,5‐Dimethylpyrazolate Cages ‐ Herbert Schumann Revisited

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