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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
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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.
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128
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134
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33846800755
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This thermodynamic invariance is consistent with similarity of BDE's 10 of HC(O, F (119) and Ph, F 126 kcal/mol
-
10 of HC(O) - F (119) and Ph - F (126 kcal/mol).
-
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135
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33846835723
-
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6 with net, favorable solvation energy being ∼20 kcal/ mol greater for the anionic derivatives.
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6 with net, favorable solvation energy being ∼20 kcal/ mol greater for the anionic derivatives.
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148
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33846825331
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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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149
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33846850954
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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.
-
-
-
-
150
-
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33846803304
-
-
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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151
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0003626507
-
-
version. 5.27, November, The Cambridge Crystallographic Data Centre: Cambridge, U.K
-
The Cambridge Structural Database, version. 5.27, November 2005; The Cambridge Crystallographic Data Centre: Cambridge, U.K., 2006.
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(2005)
The Cambridge Structural Database
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-
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153
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33846832877
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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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154
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84963455376
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33846824089
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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.
-
-
-
-
161
-
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33846791163
-
-
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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-
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162
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8844258769
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Caddick, S.; Cloke, F. G. N.; Hitchcock, P. B.; Lewis, A. K. de K. Angew. Chem., Int. Ed. 2004, 43, 5824-5827.
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164
-
-
33846792357
-
-
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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165
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33846787838
-
-
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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