Carbon-hydrogen activation of arenes and substituted arenes by the yttrium hydride (Cp*2YH)2: competition between Cp* ligand metalation, arene metalation, and hydrogen/deuterium exchange. Molecular structures of Cp*2Y(.mu.-H)(.mu.-.eta.1,.eta.5-CH2C5Me4)YCp* and Cp*2Y(o-C6H4PPh2CH2)

Booij, Marianne; Deelman, Berth Jan; Duchateau, Robbert; Postma, D.S.; Meetsma, Auke; Teuben, Jan H.

doi:10.1021/om00033a027

Cited by 135 publications

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“…The h 1 ,h 5 -coordination mode (A) of methyl-or tert-butyl-substituted cyclopentadienyl ligands exists widely in complexes of metals of Groups 3-8. [2] The h 2 ,h 4 -mode (B) is abundant in the case of metals of Groups 4-8, [2a, 3] whereas complexes exhibiting h 4 -coordination (C) are only observed for metals of Groups 9 and 10. [2a, 4] h 2 -Coordination (D) is very rare and limited to metals of Groups 9 and 10.…”

Section: Introductionmentioning

confidence: 99%

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An Unusual Organoyttrium Alkyl Complex Containing a [C₅HMe₃(η³‐CH₂)‐C₅H₄N‐κ]⁻ Ligand and an Elusive Cyclopentadienide‐Based Scandium Tuck‐Over Zwitterion Obtained by CH Bond Activation

Jian¹,

Cui²

2011

Chemistry A European J

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The acid-base reaction between Y(CH(2)SiMe(3))(3)(thf)(2) and the pyridyl-functionalized cyclopentadienyl (Cp) ligand C(5)Me(4)H-C(5)H(4)N (1 equiv) at 0 °C afforded a mixture of two products: (η(5):κ-C(5)Me(4)-C(5)H(4)N)Y(CH(2)SiMe(3))(2)(thf) (1 a) and (η(5):κ-C(5)Me(4)-C(5)H(4)N)(2)YCH(2)SiMe(3) (1 b), in a 5:2 ratio. Addition of the same ligand (2 equiv) to Y(CH(2)SiMe(3))(3)(thf)(2), however, generated 1 b together with the novel complex 1 c, the first well defined yttrium mono(alkyl) complex (η(5):κ-C(5)Me(4)-C(5)H(4)N)[C(5)HMe(3)(η(3)-CH(2))-C(5)H(4)N-κ]Y(CH(2)SiMe(3)) containing a rare κ/η(3)-allylic coordination mode in which the C-H bond activation occurs unexpectedly with the allylic methyl group rather than conventionally on Cp ring. If the central metal was changed to lutetium, the equimolar reaction between Lu(CH(2)SiMe(3))(3)(thf)(2) and C(5)Me(4)H-C(5)H(4)N exclusively afforded the bis(alkyl) product (η(5):κ-C(5)Me(4)-C(5)H(4)N)Lu(CH(2)SiMe(3))(2)(thf) (2 a). Similarly, the reaction between the ligand (2 equiv) and Lu(CH(2)SiMe(3))(3)(thf)(2) gave the mono(alkyl) complex (η(5):κ-C(5)Me(4)-C(5)H(4)N)(2)LuCH(2)SiMe(3) (2 b), in which no ligand redistribution was observed. Strikingly, treatment of Sc(CH(2)SiMe(3))(3)(thf)(2) with C(5)Me(4)H-C(5)H(4)N in either 1:1 or 1:2 ratio at 0 °C generated the first cyclopentadienide-based scandium zwitterionic "tuck-over" complex 3, (η(5):κ-C(5)Me(4)-C(5)H(4)N)Sc(thf)[μ-η(5):η(1):κ-C(5)Me(3)(CH(2))-C(5)H(4)N]Sc(CH(2)SiMe(3))(3). In the zwitterion, the dianionic ligand [C(5)Me(3)(CH(2))-C(5)H(4)N](2-) binds both to Sc1(3+) and to Sc2(3+), in η(5) and η(1)/κ modes. In addition, the reaction chemistry, the molecular structures, and the mechanism are also discussed in detail.

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Section: Introductionmentioning

confidence: 99%

“…Lu- 2 with C 5 Me 4 HÀC 5 H 4 N in either 1:1 or 1:2 ratio at 0 8C generated the first cyclopentadienide-based scandium zwitterionic "tuck-over" complex 3,…”

Section: Introductionmentioning

confidence: 99%

An Unusual Organoyttrium Alkyl Complex Containing a [C₅HMe₃(η³‐CH₂)‐C₅H₄N‐κ]⁻ Ligand and an Elusive Cyclopentadienide‐Based Scandium Tuck‐Over Zwitterion Obtained by CH Bond Activation

Jian¹,

Cui²

2011

Chemistry A European J

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“…[1][2][3][4][5] They have been shown to mediate a wide range of transformations of unsaturated substrates. [6][7][8][9][10][11][12][13][14][15] Enhanced reactivity of lanthanide alkyl and hydrido complexes also leads to hydrocarbon activation [16][17][18] and alkane functionalization. [19] Reactivity of lanthanide compounds is known to be driven by electrophilicity and coordination unsaturation of the metal center and can be controlled through tuning of the electronic and steric properties of the ancillary ligation.…”

Section: Introductionmentioning

confidence: 99%

Postmetallocene Lanthanide–Hydrido Chemistry: A New Family of Complexes [{Ln{(Me₃Si)₂NC(NiPr)₂}₂(μ‐H)}₂] (Ln=Y, Nd, Sm, Gd, Yb) Supported by Guanidinate Ligands—Synthesis, Structure, and Catalytic Activity in Olefin Polymerization

Trifonov¹,

Скворцов²,

Lyubov³

et al. 2006

Chemistry A European J

104

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The new family of Lewis base free hydrido complexes of rare‐earth metals supported by guanidinate ligands [{Ln{(Me3Si)2NC(NiPr)2}2(μ‐H)}2] (Ln=Y, Nd, Sm, Gd, Yb) was synthesized and structurally characterized. Single‐crystal X‐ray and solution NMR studies revealed that these complexes are dimeric in both solid state and in [D6]benzene. The dimeric hydrido complexes can adopt eclipsed (Nd, Sm, Gd) or staggered (Y, Yb, Lu) conformations depending on the metal‐atom size. Catalytic activity of these [{Ln{(Me3Si)2NC(NiPr)2}2(μ‐H)}2] complexes in the polymerization of ethylene, propylene, and styrene has been investigated. Complexes of Sm and Y have high catalytic activity in ethylene polymerization (1268 and 442 g mmol−1 atm−1 h−1, respectively).

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“…(C 5 Me 5 ) 2 Y(CH 2 C 6 H 5 ) (0.029 g, 86%) identified by 1 H NMR spectroscopy in C 6 D 12 (20). To further confirm the presence of (C 5 355 mmol) in 10 ml of toluene, the slurry changed from dark red to a bright orange and then back to a dark red.…”

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confidence: 99%

C–H bond activation through steric crowding of normally inert ligands in the sterically crowded gadolinium and yttrium (C ₅ Me ₅ ) ₃ M complexes

Evans

Davis

Champagne

et al. 2006

Proc. Natl. Acad. Sci. U.S.A.

113

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Synthesis of the sterically crowded Tris(pentamethylcyclopentadienyl) lanthanide complexes, (C 5Me5)3Ln, has demonstrated that organometallic complexes with unconventionally long metal ligand bond lengths can be isolated that provide options to develop new types of ligand reactivity based on steric crowding. Previously, the (C 5Me5)3M complexes were known only with the larger lanthanides, La-Sm. The synthesis of even more crowded complexes of the smaller metals Gd and Y is reported here. These complexes allow an evaluation of the size͞reactivity correlations previously limited to the larger metals and demonstrate a previously undescribed type of C 5Me5-based reaction, namely C-H bond activation. (C 5Me5)3Gd, was prepared from GdCl3 through (C 5Me5)2GdCl2K(THF)2, (C5Me5)2Gd(C3H5), and [(C5Me5)2Gd][BPh4] and structurally characterized by x-ray crystallography. Although Gd 3؉ is redox-inactive, (C5Me5)3Gd functions as a reducing agent in reactions with 1,3,5,7-cyclooctatetraene (COT) and triphenylphosphine selenide to make (C 5Me5)Gd(C8H8), [(C5Me5)2Gd]2Se2, and [(C 5Me5)2Gd]2Se depending on the stoichiometry used. When the analogous synthetic method was attempted with yttrium in arene solvents, the previously characterized (C 5Me5)2YR complexes (R‫؍‬C 6H5, CH2C6H5) were isolated instead, i.e., C-H bond activation of solvent occurred. To avoid this problem, (C 5Me5)3Y was synthesized in high yield from [(C 5Me5)2YH]2 and tetramethylfulvene in aliphatic solvents. Isolated (C 5Me5)3Y was found to metalate benzene and toluene with concomitant formation of C 5Me5H, a reaction contrary to the normal pK a values of these hydrocarbons. In this case, the normally inert (C 5Me5) 1؊ ligand engages in C-H bond activation due to the extreme steric crowding.sterically induced reduction ͉ lanthanide ͉ pentamethylcyclopentadienyl ͉ arene activation ͉ long-bond organometallics

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Carbon-hydrogen activation of arenes and substituted arenes by the yttrium hydride (Cp2YH)2: competition between Cp ligand metalation, arene metalation, and hydrogen/deuterium exchange. Molecular structures of Cp2Y(.mu.-H)(.mu.-.eta.1,.eta.5-CH2C5Me4)YCp and Cp*2Y(o-C6H4PPh2CH2)

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Cited by 135 publications

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An Unusual Organoyttrium Alkyl Complex Containing a [C₅HMe₃(η³‐CH₂)‐C₅H₄N‐κ]⁻ Ligand and an Elusive Cyclopentadienide‐Based Scandium Tuck‐Over Zwitterion Obtained by CH Bond Activation

An Unusual Organoyttrium Alkyl Complex Containing a [C₅HMe₃(η³‐CH₂)‐C₅H₄N‐κ]⁻ Ligand and an Elusive Cyclopentadienide‐Based Scandium Tuck‐Over Zwitterion Obtained by CH Bond Activation

Postmetallocene Lanthanide–Hydrido Chemistry: A New Family of Complexes [{Ln{(Me₃Si)₂NC(NiPr)₂}₂(μ‐H)}₂] (Ln=Y, Nd, Sm, Gd, Yb) Supported by Guanidinate Ligands—Synthesis, Structure, and Catalytic Activity in Olefin Polymerization

C–H bond activation through steric crowding of normally inert ligands in the sterically crowded gadolinium and yttrium (C ₅ Me ₅ ) ₃ M complexes

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Carbon-hydrogen activation of arenes and substituted arenes by the yttrium hydride (Cp*2YH)2: competition between Cp* ligand metalation, arene metalation, and hydrogen/deuterium exchange. Molecular structures of Cp*2Y(.mu.-H)(.mu.-.eta.1,.eta.5-CH2C5Me4)YCp* and Cp*2Y(o-C6H4PPh2CH2)

Abstract: Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.

Cited by 135 publications

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An Unusual Organoyttrium Alkyl Complex Containing a [C5HMe3(η3‐CH2)‐C5H4N‐κ]− Ligand and an Elusive Cyclopentadienide‐Based Scandium Tuck‐Over Zwitterion Obtained by CH Bond Activation

An Unusual Organoyttrium Alkyl Complex Containing a [C5HMe3(η3‐CH2)‐C5H4N‐κ]− Ligand and an Elusive Cyclopentadienide‐Based Scandium Tuck‐Over Zwitterion Obtained by CH Bond Activation

Postmetallocene Lanthanide–Hydrido Chemistry: A New Family of Complexes [{Ln{(Me3Si)2NC(NiPr)2}2(μ‐H)}2] (Ln=Y, Nd, Sm, Gd, Yb) Supported by Guanidinate Ligands—Synthesis, Structure, and Catalytic Activity in Olefin Polymerization

C–H bond activation through steric crowding of normally inert ligands in the sterically crowded gadolinium and yttrium (C 5 Me 5 ) 3 M complexes

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Carbon-hydrogen activation of arenes and substituted arenes by the yttrium hydride (Cp2YH)2: competition between Cp ligand metalation, arene metalation, and hydrogen/deuterium exchange. Molecular structures of Cp2Y(.mu.-H)(.mu.-.eta.1,.eta.5-CH2C5Me4)YCp and Cp*2Y(o-C6H4PPh2CH2)

An Unusual Organoyttrium Alkyl Complex Containing a [C₅HMe₃(η³‐CH₂)‐C₅H₄N‐κ]⁻ Ligand and an Elusive Cyclopentadienide‐Based Scandium Tuck‐Over Zwitterion Obtained by CH Bond Activation

An Unusual Organoyttrium Alkyl Complex Containing a [C₅HMe₃(η³‐CH₂)‐C₅H₄N‐κ]⁻ Ligand and an Elusive Cyclopentadienide‐Based Scandium Tuck‐Over Zwitterion Obtained by CH Bond Activation

Postmetallocene Lanthanide–Hydrido Chemistry: A New Family of Complexes [{Ln{(Me₃Si)₂NC(NiPr)₂}₂(μ‐H)}₂] (Ln=Y, Nd, Sm, Gd, Yb) Supported by Guanidinate Ligands—Synthesis, Structure, and Catalytic Activity in Olefin Polymerization

C–H bond activation through steric crowding of normally inert ligands in the sterically crowded gadolinium and yttrium (C ₅ Me ₅ ) ₃ M complexes