‘Agostic’ metal–alkenyl β-CH interaction in (C5H4Me)2ZrCl(CHCMe)ZrCl(C5H5)2

Erker, Gerhard; Frömberg, Wolfgang; Angermund, Klaus; Schlund, Rüger

doi:10.1039/c39860000372

Cited by 44 publications

(15 citation statements)

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“…Notable features of the NMR spectra are the resonances appearing at δ 44.2 ( J CH = 156 and 107 Hz) in the 13 C NMR spectrum and that observed at δ −9.33 in the 1 H NMR spectrum. The C(sp 2 )−H coupling constant of 107 Hz lie within the range of those of structurally well-established agostic complexes …”

supporting

confidence: 66%

Formation of Novel Trinuclear μ₃-s-cis-η²:η²-1,3-Diene Complexes of Ruthenium Having an Agostic Ru−H−C Interaction. Direct Evidence for Diene Activation in Cooperation with the Three Metal Centers

1996

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supporting

confidence: 66%

Formation of Novel Trinuclear μ₃-s-cis-η²:η²-1,3-Diene Complexes of Ruthenium Having an Agostic Ru−H−C Interaction. Direct Evidence for Diene Activation in Cooperation with the Three Metal Centers

1996

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“…H β is detected around δ 8 . Agostic homo- and heterobimetallic vinylzirconium complexes have produced related spectrocopic data . Thus, such a β-agostic vinyl interaction best fits the data for electrophilic, otherwise unsaturated 3a - H + .…”

Section: Resultsmentioning

confidence: 70%

Structure and Reactivity of η²(3e)-Nitrile and η²(3e)-Alkyne Complexes of Niobium

et al. 1999

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Nitrile adducts of the type Tp*Nb(CO)(PhC⋮CMe)(RC⋮Ν) (Tp* = hydridotris(3,5-dimethylpyrazolyl)borate; R = Me (2a), Et (2b), PhCH2 (2c), 4-MeOC6H5 (2d), Ph (2e), 4-CF3C6H5 (2f)) have been prepared in fair yields by CO displacement from Tp*Nb(CO)2(PhC⋮CMe) (1) and fully characterized. 13C NMR spectroscopy (δ 180−190 for the nitrile and alkyne contact carbons) and X-ray crystallography (for 2b) indicate an η2-coordination and an unprecedented formally three-electron-donor (3e) behavior for both the alkyne and the nitrile. Electrochemical studies suggest that an equilibrium between this η2(3e)-nitrile/η2(3e)-alkyne form and an otherwise undetected η1(2e)-nitrile/η2(4e)-alkyne form exists in solution. PhC⋮N is thermally displaced from 2e by PMe2Ph or PhC⋮CMe to give Tp*Nb(CO)(PhC⋮CMe)(PMe2Ph) or Tp*Nb(CO)(PhC⋮CMe)2 (3a), respectively. 3a does not react with PMe2Ph. Protonation of 2b with HBF4 induces nitrile/alkyne coupling to give the niobacycle Tp*NbF(CPhCMeCPhNH), via the isolated η2-iminoacyl alkyne cation [Tp*Nb(CO)(η2-CPhNH)(PhC⋮CMe)][BF4], characterized by NMR spectroscopy at 243 K. Protonation of 3a with HBF4 leads to the niobacycle Tp*NbF[C(Ph)C(Me)C(CMeCPhH)O] (X-ray structure), in which CO is included in the alkyne coupling reaction. The intermediate [Tp*Nb(CO)(CMeCPhH)(PhC⋮CMe)][BF4] has been characterized by NMR at 193 K. A deshielded Cα (δ 205), a shielded Cβ (δ 97), and a reduced 1 J CH (114 Hz) suggest that a β-CH agostic interaction stabilizes this vinyl alkyne cation. Protonation of the new phosphinoalkyne derivative Tp*Nb(CO)(PhC⋮CMe)(PPh2C⋮CPh) affords the stable phosphonium complex {Tp*Nb(CO)[Ph2P(H)C⋮CPh](PhC⋮CMe)}[BF4], in which the two alkyne ligands act as 3e donors.

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“…A, c = 6.998 (1) A, a = 96. 20 (1)°, ß = 109.63 (2)°, 7 = 91.91 (2)°; V = 1108.9 A3; R = 0.067 and Pw = 0.081 for the 2864 reflections having F2 > 3 ( 02). Crystal data for VIII: space group PI; Z = 4; a = 13.729…”

Section: Introductionmentioning

confidence: 99%

Synthesis and spectroscopic properties of tantalum .mu.-alkylidyne compounds containing bulky aryl oxide ligands: x-ray structures of the asymmetric derivatives (Me2SiCH2)2Ta(.mu.-CSiMe3)2Ta(CH2SiMe3)(OC6H3Ph2-2,6) and (Me2SiCH2)2Ta(.mu.-CSiMe3)2Ta[OC6H3(CMe3)2-2,6]2

Fanwick¹,

Ogilvy²,

Rothwell³

1987

Organometallics

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‘Agostic’ metal–alkenyl β-CH interaction in (C₅H₄Me)₂ZrCl(CHCMe)ZrCl(C₅H₅)₂

Cited by 44 publications

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Formation of Novel Trinuclear μ₃-s-cis-η²:η²-1,3-Diene Complexes of Ruthenium Having an Agostic Ru−H−C Interaction. Direct Evidence for Diene Activation in Cooperation with the Three Metal Centers

Formation of Novel Trinuclear μ₃-s-cis-η²:η²-1,3-Diene Complexes of Ruthenium Having an Agostic Ru−H−C Interaction. Direct Evidence for Diene Activation in Cooperation with the Three Metal Centers

Structure and Reactivity of η²(3e)-Nitrile and η²(3e)-Alkyne Complexes of Niobium

Synthesis and spectroscopic properties of tantalum .mu.-alkylidyne compounds containing bulky aryl oxide ligands: x-ray structures of the asymmetric derivatives (Me2SiCH2)2Ta(.mu.-CSiMe3)2Ta(CH2SiMe3)(OC6H3Ph2-2,6) and (Me2SiCH2)2Ta(.mu.-CSiMe3)2Ta[OC6H3(CMe3)2-2,6]2

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‘Agostic’ metal–alkenyl β-CH interaction in (C5H4Me)2ZrCl(CHCMe)ZrCl(C5H5)2

Cited by 44 publications

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Formation of Novel Trinuclear μ3-s-cis-η2:η2-1,3-Diene Complexes of Ruthenium Having an Agostic Ru−H−C Interaction. Direct Evidence for Diene Activation in Cooperation with the Three Metal Centers

Formation of Novel Trinuclear μ3-s-cis-η2:η2-1,3-Diene Complexes of Ruthenium Having an Agostic Ru−H−C Interaction. Direct Evidence for Diene Activation in Cooperation with the Three Metal Centers

Structure and Reactivity of η2(3e)-Nitrile and η2(3e)-Alkyne Complexes of Niobium

Synthesis and spectroscopic properties of tantalum .mu.-alkylidyne compounds containing bulky aryl oxide ligands: x-ray structures of the asymmetric derivatives (Me2SiCH2)2Ta(.mu.-CSiMe3)2Ta(CH2SiMe3)(OC6H3Ph2-2,6) and (Me2SiCH2)2Ta(.mu.-CSiMe3)2Ta[OC6H3(CMe3)2-2,6]2

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‘Agostic’ metal–alkenyl β-CH interaction in (C₅H₄Me)₂ZrCl(CHCMe)ZrCl(C₅H₅)₂

Formation of Novel Trinuclear μ₃-s-cis-η²:η²-1,3-Diene Complexes of Ruthenium Having an Agostic Ru−H−C Interaction. Direct Evidence for Diene Activation in Cooperation with the Three Metal Centers

Formation of Novel Trinuclear μ₃-s-cis-η²:η²-1,3-Diene Complexes of Ruthenium Having an Agostic Ru−H−C Interaction. Direct Evidence for Diene Activation in Cooperation with the Three Metal Centers

Structure and Reactivity of η²(3e)-Nitrile and η²(3e)-Alkyne Complexes of Niobium