Generation, alkyne cycloaddition, arene carbon-hydrogen activation, nitrogen-hydrogen activation and dative ligand trapping reactions of the first monomeric imidozirconocene (Cp2Zr:NR) complexes

Walsh, Patrick J.; Hollander, Frederick J.; Bergman, Robert G.

doi:10.1021/ja00234a043

Cited by 387 publications

(282 citation statements)

References 2 publications

(3 reference statements)

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“…1 H NMR spectroscopy performed on the remaining solution showed the formation of an intractable mixture of products, implying that ethylene oxide accessed different reactivity than the other epoxides in this study.…”

Section: Reactions With Other Strained Heterocyclic Systemsmentioning

confidence: 81%

“…The mother liquor was decanted, the solid was washed quickly with cold pentane, and the volatile materials were removed in vacuo to leave the red solid (38 mg, 44%). 1 …”

Section: Metallacyclementioning

confidence: 99%

“…The mother liquor was removed by pipet, and the residual solvent was removed from the crystals in vacuo, yielding 32 mg (81%). 1 …”

Section: P-trifluoromethylstyrene Oxide Metallacyclementioning

confidence: 99%

“…A 1 H NMR spectrum showed amino alcohols 21 and 22 and tert-butylamine (>90% purity). Spectral information for 21: 1 …”

Section: Metallacycles 6 Andmentioning

confidence: 99%

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Synthetic and Mechanistic Studies of Strained Heterocycle Opening Reactions Mediated by Zirconium(IV) Imido Complexes

et al. 2005

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The reactions of the bis(cyclopentadienyl)(tert-butylimido)zirconium complex (Cp 2 Zr=N-t-Bu) (THF) (1) with epoxides, aziridines, and episulfides were investigated. Heterocycles without accessible β-hydrogens undergo insertion/protonation of the C-X bond to produce 1,2-amino alcohols (X = O) and 1,2-diamines (X = NR), whereas heterocycles with accessible β-hydrogens undergo elimination/protonation to produce allylic alcohols (X = O) and allylic sulfides (X = S). Mechanistic investigations support a stepwise pathway with zwitterionic intermediates for the first reaction class and a concerted pathway for the second reaction class. Additionally, the feasibility of chirality transfer from the planar-chiral ebthi (ebthi = ethylenebis(tetrahydroindenyl)) ligand was demonstrated with a chiral analogue, (ebthi)-Zr=NAr(THF) (Ar = 2,6-dimethylphenyl), 2, through the diastereoselective ring opening of meso epoxides.

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Section: Reactions With Other Strained Heterocyclic Systemsmentioning

confidence: 81%

“…The mother liquor was decanted, the solid was washed quickly with cold pentane, and the volatile materials were removed in vacuo to leave the red solid (38 mg, 44%). 1 …”

Section: Metallacyclementioning

confidence: 99%

“…The mother liquor was removed by pipet, and the residual solvent was removed from the crystals in vacuo, yielding 32 mg (81%). 1 …”

Section: P-trifluoromethylstyrene Oxide Metallacyclementioning

confidence: 99%

“…A 1 H NMR spectrum showed amino alcohols 21 and 22 and tert-butylamine (>90% purity). Spectral information for 21: 1 …”

Section: Metallacycles 6 Andmentioning

confidence: 99%

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Synthetic and Mechanistic Studies of Strained Heterocycle Opening Reactions Mediated by Zirconium(IV) Imido Complexes

et al. 2005

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“…For the nitrosyl species, SBM is slightly more accessible, while OA/RE is preferred with the anionic CO analogue. 34 The major geometric differences between the SBM transition state and OA/RE intermediate are in the C-W-C angles (40)(41)(42)(43)(44)(45)(46)(47)(48)(49)(50) • wider in the OA intermediate) and W ◊ ◊ ◊ H distances (ca. 0.1 Å shorter in the OA intermediate).…”

Section: Sbm At L N M=cr 2 and L N M≡cr Bondsmentioning

confidence: 99%

Mechanisms of C–H bond activation: rich synergy between computation and experiment

et al. 2009

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Image reproduced with permission of Christophe CoperetPapers published in this issue include:A combined picture from theory and experiments on water oxidation, oxygen reduction and proton pumping Per E. M. Siegbahn and Margareta R. A. Blomberg, Dalton Trans., 2009, DOI: 10.1039 Recent computational studies of C-H bond activation at late transition metal systems are discussed and processes where lone pair assistance via heteroatom co-ligands or carboxylates are highlighted as a particularly promising means of cleaving C-H bonds. The term 'ambiphilic metal ligand activation' (AMLA) is introduced to describe such reactions.

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Substituent effects on methane activation and elimination by high-valent Zr complexes

Cundari

Curtiss

1996

Int. J. Quantum Chem.

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=A computational study of substituent effects on methane activation and elimination by high-valent zirconium complexes is reported. Substituent ( Z ) effects (in a structural, electronic, and enthalpic sense) are substantially less important for the imido (L,Zr = NZ) and imidolike TS than the amido ( L , M-NHZ). For the microscopic reverse reaction, methane CH activation, it suggests that tailoring imido reactivity through electronic modification of nitrogen substituents will be difficult. Analysis of the earliest part of the reaction coordinate for methane elimination entails structural deformation of the Zr-amido to assume an appropriate geometry for elimination, which, in some cases, is directly reflected in substantially higher elimination barriers. Lower elimination barriers correlate with stronger agostic bonding, providing further support for the crucial importance of agostic bonding in facilitating alpha-elimination processes for high-valent transition-metal complexes. 0 1996 John Wiley & Sons, Inc.cal vapor deposition (CVD) of solid-state oxides, carbides, and nitrides, from organometallic precursors [2]. In the prototypical reaction (11,

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Generation, alkyne cycloaddition, arene carbon-hydrogen activation, nitrogen-hydrogen activation and dative ligand trapping reactions of the first monomeric imidozirconocene (Cp2Zr:NR) complexes

Cited by 387 publications

References 2 publications

Synthetic and Mechanistic Studies of Strained Heterocycle Opening Reactions Mediated by Zirconium(IV) Imido Complexes

Synthetic and Mechanistic Studies of Strained Heterocycle Opening Reactions Mediated by Zirconium(IV) Imido Complexes

Mechanisms of C–H bond activation: rich synergy between computation and experiment

Substituent effects on methane activation and elimination by high-valent Zr complexes

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