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Volumn 15, Issue 29, 2009, Pages 7063-7073

Mechanisms in the reaction of palladium(II)-π-Allyl complexes with aryl halides: Evidence for NHC exchange between two palladium complexes

Author keywords

Carbene ligands; Density functional calculations; Palladium; Transmetalation

Indexed keywords

ALLYL COMPLEXES; ARYL ELECTROPHILES; ARYL HALIDES; AUTOCATALYTIC; BOND METATHESIS; CARBENE LIGANDS; DENSITY FUNCTIONAL CALCULATIONS; DFT STUDY; PALLADIUM COMPLEXES; PHOSPHANE; RATE DETERMINING STEP; TRANSMETALATION;

EID: 67650641839     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200900373     Document Type: Article
Times cited : (34)

References (108)
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    • Despite the likely binding of 2-propenylimidazolium to 3a, as suggested by DFT calculations, we use the term "monoligated" to mark the difference with catalysts containing two more strongly binding ligands.
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    • One referee suggested we conducted the calculations using an explicit solvent molecule or continuum solvent approach. We conducted a test calculation on the step L-→ M+ N and found that the PCM model, using CH 2Cl2 as solvent gave a 9.1 kcal mol-1 energy difference against 11.2kcal mor-1 in the gas phase. Therefore we believe that in this case the gas phase calculations give acceptable results
    • -1 in the gas phase. Therefore we believe that in this case the gas phase calculations give acceptable results.
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    • One referee suggested that the complex could be activated by reductive elimination of the phosphonium salt allyl-PCy3, Such reactions have been observed with bis-phosphane complexes, see C. Amatore, A. Jutand, M. A. M. Barki, G. Meyer, L. Mottier, Eur. J. Inorg. Chem. 2001, 873-880
    • +. Such reactions have been observed with bis-phosphane complexes, see C. Amatore, A. Jutand, M. A. M. Barki, G. Meyer, L. Mottier, Eur. J. Inorg. Chem. 2001, 873-880.
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    • However, we did not observe such species by ESI/MS, see ref. [45], see the Supporting Information.
    • However, we did not observe such species by ESI/MS, see ref. [45], see the Supporting Information.
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    • Although in the case of PCy3, the energy difference is only 1.1 kcal.mol-1, see the Supporting Information
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    • Although the complex resulting from the second oxidative addition is the same as that resulting from the first oxidative addition, in the first case I is formed together with 2-propenylimidazolium wheras 2arylimidazolium is liberated in the second case, hence the different name
    • Although the complex resulting from the second oxidative addition is the same as that resulting from the first oxidative addition, in the first case I is formed together with 2-propenylimidazolium wheras 2arylimidazolium is liberated in the second case, hence the different name.
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    • This is consistent with the fact that we failed to isolate the phenyl analogue of 7a due to extensive decomposition to Pd black: A. T. Normand, PhD Thesis, Cardiff University UK, 2007
    • This is consistent with the fact that we failed to isolate the phenyl analogue of 7a due to extensive decomposition to Pd black: A. T. Normand, PhD Thesis, Cardiff University (UK), 2007.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.