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Volumn 129, Issue 5, 2007, Pages 1342-1358

Aryl-fluoride reductive elimination from Pd(II): Feasibility assessment from theory and experiment

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; FLUORIDE MINERALS; HYDROGEN BONDS; PROBABILITY DENSITY FUNCTION; REDUCTION; STOICHIOMETRY; THERMODYNAMIC PROPERTIES;

EID: 33846796141     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja066930l     Document Type: Article
Times cited : (124)

References (193)
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    • ‡ (vide infra, Figure 9); in all other computed three-coordinate Pd(II) derivatives and transition states for reductive elimination of Ar-X auxiliary ligand hydrogens do not approach the metal closer than 2.7 Å. Cartesian coordinates and drawings with close contacts highlighted are provided in Supporting Information.
    • ‡ (vide infra, Figure 9); in all other computed three-coordinate Pd(II) derivatives and transition states for reductive elimination of Ar-X auxiliary ligand hydrogens do not approach the metal closer than 2.7 Å. Cartesian coordinates and drawings with close contacts highlighted are provided in Supporting Information.
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    • 1c and numerous other circumstances: Schwesinger, R.; Link, R.; Wenzl, P.; Kossek, S. Chem. - Eur. J. 2006, 12, 438-445.;
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    • Cl, compares well with the value of 9.4 kcal/mol obtained for this process in a different computational study: Green, J. C.; Herbert, B. J.; Lonsdale, R. J. Organomet. Chem. 2005, 690, 6054-6067.
    • Cl, compares well with the value of 9.4 kcal/mol obtained for this process in a different computational study: Green, J. C.; Herbert, B. J.; Lonsdale, R. J. Organomet. Chem. 2005, 690, 6054-6067.
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    • Contributing resonance forms have been identified on the basis of computed geometrical parameters only, available in Supporting Information. Mixed resonance form assignments do not bear any quantitative connotation
    • Contributing resonance forms have been identified on the basis of computed geometrical parameters only, available in Supporting Information. Mixed resonance form assignments do not bear any quantitative connotation.
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    • 10 of HC(O) - F (119) and Ph - F (126 kcal/mol).
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    • 6 with net, favorable solvation energy being ∼20 kcal/ mol greater for the anionic derivatives.
    • 6 with net, favorable solvation energy being ∼20 kcal/ mol greater for the anionic derivatives.
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    • It appears reasonable to expect bridge cleavage leading to the formation of a T-shaped PdAr(μ-F)L fragment with L trans to the vacant site to proceed in a concerted manner with its isomerization to the more sterically stable geometry with Ar trans to the vacant site, i.e. that processes a′ and b in Scheme 2 and the like occur together in a single elementary step.
    • It appears reasonable to expect bridge cleavage leading to the formation of a T-shaped PdAr(μ-F)L fragment with L trans to the vacant site to proceed in a concerted manner with its isomerization to the more sterically stable geometry with Ar trans to the vacant site, i.e. that processes a′ and b in Scheme 2 and the like occur together in a single elementary step.
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    • Crystallographic details for [Pd(C6H4-4-NO 2)P(t-Bu)3(μ-F)]2 x (PhF)2 (18 x (PhF)2, C48H72F 4N2O4P2Pd2, 1091.82 g/mol, Monoclinic, P21/n, a, 15.473(4, b, 12.450(3, c, 26.373(7, β, 100.704(4)°, V, 4992(2) Å3, T, 99°C, Z, 4; R1, 0.0450. wR2, 0.0901, I > 2σ(I), R1, 0.0857, wR2, 0.1028 all data, GOF, 1.018
    • 3, T = -99°C, Z = 4; R1 = 0.0450. wR2 = 0.0901 ([I > 2σ(I)]); R1 = 0.0857, wR2 = 0.1028 (all data); GOF = 1.018.
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    • C-H bonds were extended to 1.083 Å for all reported H⋯X measurements.
    • C-H bonds were extended to 1.083 Å for all reported H⋯X measurements.
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    • All yields are given in Pd equivalents, i.e. 1 mol of Ar-Ar formed per 1 mol of Pd dimer corresponds to 100%. Products quantified in Schemes 4 and 5 were identified directly in the reaction mixtures by NMR and quantified by integration vs internal standard (± 5%). Products identified by GC-MS only may have originated from additional thermal reactivity at T°C of up to 280 during GC analysis. See Supporting Information for additional details.
    • All yields are given in Pd equivalents, i.e. 1 mol of Ar-Ar formed per 1 mol of Pd dimer corresponds to 100%. Products quantified in Schemes 4 and 5 were identified directly in the reaction mixtures by NMR and quantified by integration vs internal standard (± 5%). Products identified by GC-MS only may have originated from additional thermal reactivity at T°C of up to 280 during GC analysis. See Supporting Information for additional details.
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    • Although ESI-MS of the reaction mixture, after redissolution in CDCl 3, did show metalated Pd(CH2-C6H 4-2-P(o-Tolyl)2, and Pd(CH 2-C6H4-2-P(o-Tolyl)2, P(o-Tolyl)3, fragments, their presence in ESI-MS spectrum is typical of many Pd(P(o-Tolyl)3) complexes, i.e. metalation takes place readily during ESI
    • 3) complexes, i.e. metalation takes place readily during ESI.
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    • 3 to react with low-ligated, highly reactive Pd(0) species instead.
    • 3 to react with low-ligated, highly reactive Pd(0) species instead.
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    • Both Pd fragments in the partly cleaved dimer are derived from the basic T-shaped PdAr(F)L geometry by coordination of a nucleophile to Pd or electrophile to F, modifications that were computed (Figures 2, 3) to increase the barrier to reductive elimination from that of the T-shaped precursor.
    • Both Pd fragments in the partly cleaved dimer are derived from the basic T-shaped PdAr(F)L geometry by coordination of a nucleophile to Pd or electrophile to F, modifications that were computed (Figures 2, 3) to increase the barrier to reductive elimination from that of the T-shaped precursor.
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    • Underestimation of the stability of PtBu310 NO2 relative to [PtBu310 NO2]2 and PtBu310-11NO2‡ in the computational model due to inadequate description of P(t-Bu) CH⋯Pd agostic interactions (vide supra) serves to raise ΔG1‡ approximated by ΔH°([PtBu310 NO2]2-1, but affects ΔG1/2‡ much less due to cancellation of the decrease in ΔH‡([ PtBu310NO2] 2-1) and increase in ΔG ‡-PtBu310-11 NO2‡, the difference from experi
    • ‡); the difference from experiment introduced by the systematic error of the computational model is estimated to be on the order of 5 kcal/mol.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.