A comparative study of the reactivity of Zr(IV), Hf(IV) and Th(IV) metallocene complexes: Thorium is not a Group IV metal after all

Jantunen, Kimberly C.; Scott, Brian L.; Kiplinger, Jaqueline L.

doi:10.1016/j.jallcom.2007.03.138

Cited by 39 publications

(65 citation statements)

References 67 publications

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“…The Hf−C(15/22/29) bond lengths are all comparable to Zr−C(15) in 5 Zr . The Hf−CH 2 distances are also comparable to those in the related benzyl compounds HfCp 2 (CH 2 Ph) 2 [average = 2.29(1) Å] 49 and HfCp*(CH 2 Ph) 3 [average = 2.26(3) Å]. 50 The Pn* ligand of 5a Hf has a considerably increased M− Pn* cent distance compared to 5 Zr (2.169 and 2.108 Å, respectively) as well as a relative flattening of the ligand [fold angles 24.7(6)°and 28.8(3)°, respectively].…”

Section: Organometallicssupporting

confidence: 52%

Zirconium and Hafnium Permethylpentalene Compounds

2016

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A selection of new η 8 -permethylpentalene zirconium and hafnium complexes are reported. The first d-block metal bis-(permethylpentalene) sandwich complexes, (Pn* 2 M ; Pn* = C 8 Me 6 ; M = Zr, Hf) have been synthesized and structurally characterized. The bis-allyl species Pn*M(C 3 H 5 ) 2 (M = Zr, Hf) have been synthesized; these complexes are fluxional in solution and react with CO 2 to give the double-insertion product Pn*M(κ 2 -O 2 CCH 2 CHCH 2 ) 2 (M = Zr, Hf). We also report monometallic, bimetallic, and polymeric σ-bonded alkyl derivatives such as (Pn*Zr) 2 (μ-CH 2 )(μ-Me) 2 , [Pn*Hf(CH 2 Ph) 3 ][Li(1,4-dioxane) 4 ], and [Pn*ZrPh(μ-Ph) 2 Li(μ-1,4-dioxane)] n .

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Section: Organometallicssupporting

confidence: 52%

Zirconium and Hafnium Permethylpentalene Compounds

2016

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“…A related catalytic version of this reaction appeared recently . Remarkably, [Cp′ 2 ZrMe 2 ] does not react with pyridine even under harsh conditions . Dihydrocarbyl group 4 metallocenes can also activate C−H bonds by a reversible β‐H abstraction sequence .…”

Section: Introductionmentioning

confidence: 99%

“…[9] Remarkably,[ Cp' 2 ZrMe 2 ]d oes not react with pyridine even under harsh conditions. [10] Dihydrocarbyl group 4m etallocenes can also activate CÀHb onds by ar eversible b-H abstractions equence. [11] The transient reactive intermediates that contain h 2alkene, h 2 -alkyne or h 2 -benzyne ligands can react with av ariety of unsaturated substrates, forming metallacycles originating from formal insertion/oxidative coupling reactions.…”

Section: Introductionmentioning

confidence: 99%

Coupling and Dearomatization of Pyridines at a Transient η²‐Cyclopropene/Bicyclobutane Zirconocene Complex

Romero

Dufrois

Vendier

et al. 2017

Chemistry A European J

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This paper reports on stereospecific coupling reactions between an η -cyclopropene ligand and pyridine derivatives, which are preferred to alternative C-H bond activation reactions. The dicyclopropylzirconocene complex [Cp Zr(c-C H ) ] (1) eliminates cyclopropane to generate the η -cyclopropene/bicyclobutane intermediate [Cp Zr(η -c-C H )] (A). A does not activate any pyridine C-H bonds, but rather pyridine inserts into a Zr-C bond of A, yielding an azazirconacycle with a dearomatized pyridyl group [Cp Zr{κ -N,C -(2-c-C H )-C H N}] (2). Kinetic data, isotopelabelling experiments, and DFT calculations indicate that the rate-determining step of this stereospecific reaction is cyclopropane elimination, and that the stability of the intermediate [Cp Zr(η -c-C H )(NC H )] (A-py) governs the selectivity of the reaction. Complex 2 tautomerizes to [Cp Zr{κ -N,C -(2-C H )-C H N}] (6) through a base-catalyzed proton migration accompanied by cyclopropyl opening and restoration of conjugation within the zirconacycle.

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“…[5] Till this day the discussion is vivid whether Th IV has to be considered as an actinide element or as a large member of the group IV elements, with recent contributions on the chemistry of the complexes [(Cp*) 2 M(Me) 2 ] (M = Zr, Hf, Th), [6] on quantum chemical calculations on the Cp derivatives [(Cp) 2 M(Me) 2 ] (M = Zr, Th, U), [7] or on spectroscopic similarities and differences. [8] Recently, our group reported on the 5,5Ј-bitetrazole coordination chemistry of a number of trivalent 4f element ions.…”

Section: Introductionmentioning

confidence: 99%

A New 5,5′‐Bitetrazole Thorium(IV) Compound: Synthesis, Crystal Structure and Quantum Chemical Investigation

et al. 2009

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[a][ ‡]Keywords: Actinides / Bitetrazole / Hydrates / Thorium / X-ray diffraction / Density functional calculations Thorium(IV) 5,5Ј-bitetrazolate hydrate C 4 H 26 N 16 O 13 Th has been prepared and structurally analysed by single crystal XRD. The compound crystallises in the triclinic space group P1 with the cell constants a = 1058.2(2), b = 1081.6(2), c = 1136.7(2) pm, α = 73.46(2), β = 83.98(2), γ = 66.01(2)°. The observed structure is similar to the salt-like structures of the corresponding Tb III and Er III systems with respect to the noncoordinating behaviour of the 5,5Ј-bitetrazolate dianions. The Th IV cations form discrete hydroxo-bridged binuclear thorium-aqua complexes with Th-Th distances of 399 (7) pm.

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A comparative study of the reactivity of Zr(IV), Hf(IV) and Th(IV) metallocene complexes: Thorium is not a Group IV metal after all

Cited by 39 publications

References 67 publications

Zirconium and Hafnium Permethylpentalene Compounds

Zirconium and Hafnium Permethylpentalene Compounds

Coupling and Dearomatization of Pyridines at a Transient η²‐Cyclopropene/Bicyclobutane Zirconocene Complex

A New 5,5′‐Bitetrazole Thorium(IV) Compound: Synthesis, Crystal Structure and Quantum Chemical Investigation

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A comparative study of the reactivity of Zr(IV), Hf(IV) and Th(IV) metallocene complexes: Thorium is not a Group IV metal after all

Cited by 39 publications

References 67 publications

Zirconium and Hafnium Permethylpentalene Compounds

Zirconium and Hafnium Permethylpentalene Compounds

Coupling and Dearomatization of Pyridines at a Transient η2‐Cyclopropene/Bicyclobutane Zirconocene Complex

A New 5,5′‐Bitetrazole Thorium(IV) Compound: Synthesis, Crystal Structure and Quantum Chemical Investigation

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Coupling and Dearomatization of Pyridines at a Transient η²‐Cyclopropene/Bicyclobutane Zirconocene Complex