Organolanthanide-catalysed oligomerisation of 2-cycloalken-1-ones

Deelman, Berth‐Jan; Bijpost, Erik A.; Teuben, Jan H.

doi:10.1039/c39950001741

Cited by 28 publications

(38 citation statements)

References 6 publications

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“…It is likely that activation of H−X and C−X bonds (X = O, N, S, halogen) is favored by initial coordination of the heteroatom ligand to the metal complex, thus leading to the formation of the [Ln]−X bond. Activation of C−H bonds can produce either H/H exchange or metalation reactions; extended Hückel calculations showed, in agreement with the reactions observed between the complexes Cp* 2 LnH (Ln = Sc, Y, Lu) and hydrocarbons RH, that H/H exchange is easier for R = aryl than for R = alkyl because an sp 2 carbon can better stabilize the [H-R-H] - moiety in the transition state …”

Section: σ-Bond Metathesis Reactionssupporting

confidence: 70%

Synthesis, Structure, and Reactions of Hydride, Borohydride, and Aluminohydride Compounds of the f-Elements

1997

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Section: σ-Bond Metathesis Reactionssupporting

confidence: 70%

Synthesis, Structure, and Reactions of Hydride, Borohydride, and Aluminohydride Compounds of the f-Elements

1997

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“…(3). Substitution at the carbon or replacement of CH 3 by groups like SiR 3 or a phenyl group which better stabilize a more hypervalent anion 46 could make H exchange in eqn. (3) accessible.…”

Section: Discussionmentioning

confidence: 99%

DFT study of CH4 activation by d0 Cl2LnZ (Z = H, CH3) complexes

Maron

Perrin

Eisenstein

2002

J. Chem. Soc., Dalton Trans.

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published as an Advance Article on the web 24th January 2002 DFT(B3PW91) calculations of the activation of CH 4 by models (Cl 2 LnZ) of Cp* 2 LnZ (Z = H, Me) have been carried out for the entire lanthanide series. Cl 2 LnZ appears to be a good model for Cp* 2 LnZ. It reproduces well the coordination around the lanthanide. The energetics of the transformation X 2 LnH ϩ CH 4 X 2 LnCH 3 ϩ H 2 are fairly close for X = Cl and Cp and the difference in behavior can be attributed to the stronger electron donating ability of Cp. Formation of the lanthanide hydride complex is calculated to be exothermic in agreement with experimental evidence. The energy profiles of the reactions Cl 2 LnH ϩ CH 4 Cl 2 LnCH 3 ϩ H 2 ; Cl 2 LnH* ϩ CH 4 Cl 2 LnH ϩ H*CH 3 ; Cl 2 LnCH* 3 ϩ CH 4Cl 2 LnCH 3 ϩ H-CH* 3 have been calculated. The transition states for the first and third transformations are energetically accessible, in good agreement with the known experimental data. The second reaction has a transition state of very high energy indicating an unfeasible reaction. The geometry of the transition stuctures are suggestive of a proton transfer between two anionic species (Z and CH 3 Ϫ ; Z = H Ϫ and CH 3 Ϫ ) in the field of the lanthanide fragment.

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“…[21,22,26] Although Fe is a late transition metal, the metal does not favor a high oxidation state. For comparison, we have also studied the metathesis processes with the analogous complexes [Cp(PH 3 )FeR] (R H or CH 3 ).…”

Section: Computational Detailsmentioning

confidence: 98%

“…[21,22] For the Ru system, whose endothermicity is lower than that for Fe system, a relatively long H(1) ¥¥¥ H(2) distance (1.617 ä) and a large C-M-H(1) angle (106.38) are found in the transition state TpRuHTS. The C ¥¥¥ H(2) distance in TpRuHTS is also quite long (1.589 ä).…”

Section: Computational Detailsmentioning

confidence: 98%

Theoretical Studies on the Metathesis Processes, [Tp(PH₃)MR(η²‐HCH₃)] → [Tp(PH₃)M(CH₃)(η²‐HR)] (M=Fe, Ru, and Os; R=H and CH₃)

Lam

Jia

Lin

et al. 2003

Chemistry A European J

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Theoretical calculations on the metathesis process, [Tp(PH3)MR(eta 2-H[bond]CH3)] --> [Tp(PH3)M(CH3)(eta 2-H[bond]R)] (M=Fe, Ru, and Os; R=H and CH3), have been systematically carried out to study their detailed reaction mechanisms. Other than the one-step mechanism via a four-center transition state and the two-step mechanism through an oxidative addition/reductive elimination pathway, a new one-step mechanism, with a transition state formed under oxidative addition, has been found. Based on the intrinsic reaction coordinate calculations, we found that the trajectories of the transferring hydrogen atom in the metathesis processes studied are similar to each other regardless of the nature of reaction mechanisms.

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Organolanthanide-catalysed oligomerisation of 2-cycloalken-1-ones

Cited by 28 publications

References 6 publications

Synthesis, Structure, and Reactions of Hydride, Borohydride, and Aluminohydride Compounds of the f-Elements

Synthesis, Structure, and Reactions of Hydride, Borohydride, and Aluminohydride Compounds of the f-Elements

DFT study of CH4 activation by d0 Cl2LnZ (Z = H, CH3) complexes

Theoretical Studies on the Metathesis Processes, [Tp(PH₃)MR(η²‐HCH₃)] → [Tp(PH₃)M(CH₃)(η²‐HR)] (M=Fe, Ru, and Os; R=H and CH₃)

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Organolanthanide-catalysed oligomerisation of 2-cycloalken-1-ones

Cited by 28 publications

References 6 publications

Synthesis, Structure, and Reactions of Hydride, Borohydride, and Aluminohydride Compounds of the f-Elements

Synthesis, Structure, and Reactions of Hydride, Borohydride, and Aluminohydride Compounds of the f-Elements

DFT study of CH4 activation by d0 Cl2LnZ (Z = H, CH3) complexes

Theoretical Studies on the Metathesis Processes, [Tp(PH3)MR(η2‐HCH3)] → [Tp(PH3)M(CH3)(η2‐HR)] (M=Fe, Ru, and Os; R=H and CH3)

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Theoretical Studies on the Metathesis Processes, [Tp(PH₃)MR(η²‐HCH₃)] → [Tp(PH₃)M(CH₃)(η²‐HR)] (M=Fe, Ru, and Os; R=H and CH₃)