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

Jian, Zhongbao; Cui, Dongmei

doi:10.1002/chem.201102378

Cited by 18 publications

(7 citation statements)

References 57 publications

(60 reference statements)

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“…The CpPN ligand coordinates to the Y 3+ ion in a η 2 /κ 1 mode. The bond length of Y1–C2 (2.703(3) Å) is unexpectedly shorter than that of Y1–C1 (2.778(3) Å), but both fall in the range of the Y–C(Cp) bond. , However, the bond lengths of Y1···C3 (3.345 Å), Y1···C4 (3.729 Å), and Y1···C5 (3.424 Å) exceed the normal range, suggesting that the C3, C4, and C5 atoms are away from the metal center. Furthermore, these bond distances of C1–C2 (1.433(4) Å), C2–C3 (1.385(5) Å), C3–C4 (1.401(5) Å), C4–C5 (1.375(5) Å), and C1–C5 (1.414(5) Å) indicate that the electrons tend to delocalize within the Cp framework.…”

Section: Resultsmentioning

confidence: 93%

Yttrium Hydride Complex Bearing CpPN/Amidinate Heteroleptic Ligands: Synthesis, Structure, and Reactivity

et al. 2012

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The reaction of the yttrium dialkyls (C 5 H 4 − PPh 2 N−C 6 H 3 i Pr 2 )Y(CH 2 SiMe 3 ) 2 (thf) (1) with an excess of N,N′-diisopropylcarbodiimide gave the yttrium monoalkyl complex (C 5 H 4 −PPh 2 N−C 6 H 3 i Pr 2 )Y(CH 2 SiMe 3 )[ i PrN C(CH 2 SiMe 3 )−N i Pr] (2). 2 subsequently reacted with 1 equiv of PhSiH 3 to generate the CpPN/amidinate heteroleptic yttrium hydride {(C 5 H 4 −PPh 2 N−C 6 H 3 i Pr 2 )Y[ i PrNC-(CH 2 SiMe 3 )−N i Pr](μ-H)} 2 (3). Hydride 3 showed good reactivity toward various substrates containing unsaturated C− C, C−N, and N−N bonds, such as azobenzene, p-tolyacetylene, 1,4-bis(trimethylsilyl)-1,3-butanediyne, N,N′-diisopropylcarbodiimide, and 4-dimethylaminopyridine, affording the yttrium hydrazide complex 4 with a rare η 2 -Cp bonding mode, yttrium terminal alkynyl complex 5, yttrium η 3 -propargyl complex 6, yttrium amidinate complex 7, and yttrium 2-hydro-4dimethylaminopyridyl product 8, respectively.

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Section: Resultsmentioning

confidence: 93%

Yttrium Hydride Complex Bearing CpPN/Amidinate Heteroleptic Ligands: Synthesis, Structure, and Reactivity

et al. 2012

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“…A comparison with related 4f-arene complexes is of value: Lappert and co-workers observed no C À H bond activation in the benzene radical anion complexes such as [K( [18] [36] but spontaneous CÀC aryl coupling was observed by Fryzuk 2 ]. [37] Giambastiani and Kempe and their respective co-workers used amidopyridinate ligands to stabilize hydrocarbyl complexes of rare-earth metals: 23, 25, and 27 undergo reactions with PhSiH 3 , which proceed through s-bond metathesis to give hydrido complexes, including 24 and 26 (Scheme 8).…”

Section: Post-metallocene Complexes With Càh Interactions and Their Rmentioning

confidence: 99%

“…[17] Many Cp-supported f-block "tuck-in" and "tuck-over" complexes have now been reported. Other interesting examples (shown in Scheme 2) are the "tuck-over" zwitterionic complex [(h 5 :k-C 5 Me 4 -C 5 H 4 N)Sc(thf){m-h 5 :h 1 :k-C 5 Me 3 (CH 2 )-C 5 H 4 N}Sc(CH 2 SiMe 3 ) 3 ] (5) formed through spontaneous C À H activation of a pyridyl-functionalized Cp ligand, [18] and a "tuck-in" [(h 5 :h 1 -C 5 Me 4 SiMe 2 CH 2 )Ln(C 5 Me 4 SiMe 3 )(thf)] (6; Ln = Y, Nd, Sm, Dy, Lu). [19] Many of these molecules show interesting CÀH activation chemistry.…”

Section: Introductionmentioning

confidence: 99%

CH Bond Activation by f‐Block Complexes

et al. 2014

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Most homogeneous catalysis relies on the design of metal complexes to trap and convert substrates or small molecules to value-added products. Organometallic lanthanide compounds first gave a tantalizing glimpse of their potential for catalytic C-H bond transformations with the selective cleavage of one C-H bond in methane by bis(permethylcyclopentadienyl)lanthanide methyl [(η(5) -C5 Me5 )2 Ln(CH3 )] complexes some 25 years ago. Since then, numerous metal complexes from across the periodic table have been shown to selectively activate hydrocarbon C-H bonds, but the challenges of closing catalytic cycles still remain; many f-block complexes show great potential in this important area of chemistry.

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“…The organometallic chemistry of yttrium is dominated by cyclopentadienyl complexes and their sandwich and half-sandwich derivatives . Far less attention is given to organoyttrium compounds containing methyl, Me 3 SiCH 2 , (Me 3 Si) 2 CH, benzyl, and phenyl groups . All these organometallics show enhanced stability due to the lack of easily available β-hydrogen atoms.…”

Section: Introductionmentioning

confidence: 99%

Homoleptic Tris(α,ω-alkanediyl)yttriates of the Type [{Li(dme)}₃{Y(CH₂-X-CH₂)₃}] (X = C₂H₄, C₃H₆, Si(CH₃)₂)

et al. 2014

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The metathesis reaction of anhydrous yttrium(III) chloride with ethereal solutions of 1,4-dilithiobutane, 1,5-dilithiopentane as well as bis(lithiomethyl)dimethylsilane in the molar ratio of 1:3 yields the homoleptic yttriates [{Li(dme)} 3 {Y-(C 4 H 8 ) 3 }] (2), [{Li(dme)} 3 {Y(C 5 H 10 ) 3 }] (3), and [{Li(dme)} 3 (Y{CH 2 Si(CH 3 ) 2 CH 2 } 3 )] (4) after addition of 1,2-dimethoxyethane (DME). The molecular structures of 2 and 3 show hexa-coordinate yttrium atoms in distorted octahedral environments of three bidentate chelating α,ω-alkanediyl ligands. Three Li(dme) units occupy bridging positions between two α-CH 2 fragments of different ligands. These complexes decompose at 0 °C in THF-d 8 solution leading to the formation of methyl vinyl ether as well as n-butane and npentane, respectively. The 13 C{ 1 H} NMR experiment of 2 at −40 °C shows a doublet for the α-CH 2 fragment with a 1 J C,Y coupling constant of 21.6 Hz. For the thermally more stable complex 4 (NMR measurement at r.t.), a 1 J C,Y coupling constant of 16.9 Hz was observed. Bis(lithiomethyl)dimethylsilane crystallizes as the cage compound [(Et 2 O) 4 {(LiCH 2 ) 2 Si(CH 3 ) 2 } 3 (LiCl)] 2 (1) with a shell-like structure around the central chloride ions. YCl 3 reacts with an excess of phenyllithium in diethyl ether to a product mixture. Lithium chloride can be removed with tetrahydropyran (THP) as [(thp) 2 LiCl] 2 (5). After the addition of THF to the residue, [Ph 3 Y(thf) 3 ] (6, 1 J C,Y = 48.7 Hz) could be identified in the solution. The applicability of complexes 2, 3, and 4 as initiators for styrene polymerization is studied in THF solution at −70 °C.

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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

Cited by 18 publications

References 57 publications

Yttrium Hydride Complex Bearing CpPN/Amidinate Heteroleptic Ligands: Synthesis, Structure, and Reactivity

Yttrium Hydride Complex Bearing CpPN/Amidinate Heteroleptic Ligands: Synthesis, Structure, and Reactivity

CH Bond Activation by f‐Block Complexes

Homoleptic Tris(α,ω-alkanediyl)yttriates of the Type [{Li(dme)}₃{Y(CH₂-X-CH₂)₃}] (X = C₂H₄, C₃H₆, Si(CH₃)₂)

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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

Cited by 18 publications

References 57 publications

Yttrium Hydride Complex Bearing CpPN/Amidinate Heteroleptic Ligands: Synthesis, Structure, and Reactivity

Yttrium Hydride Complex Bearing CpPN/Amidinate Heteroleptic Ligands: Synthesis, Structure, and Reactivity

CH Bond Activation by f‐Block Complexes

Homoleptic Tris(α,ω-alkanediyl)yttriates of the Type [{Li(dme)}3{Y(CH2-X-CH2)3}] (X = C2H4, C3H6, Si(CH3)2)

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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

Homoleptic Tris(α,ω-alkanediyl)yttriates of the Type [{Li(dme)}₃{Y(CH₂-X-CH₂)₃}] (X = C₂H₄, C₃H₆, Si(CH₃)₂)