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Recently, we reported the first examples of phosphole-containing hybrid calixpyrroles. Matano, Y.; Nakabuchi, T.; Miyajima, T.; Imahori, H. Organometallics 2006, 25, 3105-3107.
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Phosphole-containing porphyrins and a P-confused carbaporphyrinoid were reported recently, (a) Delaere, D.; Nguyen, M. T. Chem. Phys. Lett. 2003, 376, 329-337.
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38349176517
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Based on the number and position of the sp3-carbons, calix[4]phyrins are divided into four classes: porphomethenes, 5,10-porphodimethenes, 5,15-porphodimethenes, and porphotrimethenes
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3-carbons, calix[4]phyrins are divided into four classes: porphomethenes, 5,10-porphodimethenes, 5,15-porphodimethenes, and porphotrimethenes.
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84
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2,S-hybrid calixphyrins, see: Matano, Y.; Miyajima, T.; Nakabuchi, T.; Imahori, H.; Ochi, N.; Sakaki, S. J. Am. Chem. Soc. 2006, 128, 11760-11761.
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In the case of X, O, stabilization attained by the π-extension of the N-O-N unit from 14π to 16π does not compensate for the large destabilization caused by the loss of the attractive hydrogen-bonding interaction in 3Om and the gain of the repulsive interaction among the lone pairs at the core in 4Om. In the case of X, NH, the highly strained conformation owing to the repulsive interaction among the NH groups in 3Nm is relaxed by dehydrogenative oxidation, and the attractive hydrogenbonding interaction arises between the lone pairs and the NH group in 4Nm. Totally, a large stabilization is gained by the π-extension of the N-N-N unit from 14π to 16π. In the case of X, S, the loss of attractive interaction in 3Sm and the gain of repulsive interaction in 4Sm would be smaller as compared to those for the furan analogues
-
In the case of X = O, stabilization attained by the π-extension of the N-O-N unit from 14π to 16π does not compensate for the large destabilization caused by the loss of the attractive hydrogen-bonding interaction in 3Om and the gain of the repulsive interaction among the lone pairs at the core in 4Om. In the case of X = NH, the highly strained conformation owing to the repulsive interaction among the NH groups in 3Nm is relaxed by dehydrogenative oxidation, and the attractive hydrogenbonding interaction arises between the lone pairs and the NH group in 4Nm. Totally, a large stabilization is gained by the π-extension of the N-N-N unit from 14π to 16π. In the case of X = S, the loss of attractive interaction in 3Sm and the gain of repulsive interaction in 4Sm would be smaller as compared to those for the furan analogues.
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94
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0005154738
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The calculated relative stabilities may also be concerned with the oxidation potentials of pyrrole, thiophene, and furan, which were reported to be +0.8, +1.6, and +1.85 V, respectively (vs. SCE). See: Tourillon, G.; Garnier, F. J. Electroanal. Chem. 1982, 135, 173-178.
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The calculated relative stabilities may also be concerned with the oxidation potentials of pyrrole, thiophene, and furan, which were reported to be +0.8, +1.6, and +1.85 V, respectively (vs. SCE). See: Tourillon, G.; Garnier, F. J. Electroanal. Chem. 1982, 135, 173-178.
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As we recalculated the NAO occupancies for 7Sm and 8S using a different basis set, the values listed in Table 2 are slightly different from those reported in ref 20.
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As we recalculated the NAO occupancies for 7Sm and 8S using a different basis set, the values listed in Table 2 are slightly different from those reported in ref 20.
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Sharp, P.R.1
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112
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38349096761
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2 was carried out in toluene, the Rh(III) complex 11 was obtained in ca. 30% yield.
-
2 was carried out in toluene, the Rh(III) complex 11 was obtained in ca. 30% yield.
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113
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Attar, S.; Bearden, W. H.; Alcock, N. W.; Alyea, E. C.; Nelson, J. H. Inorg. Chem. 1990, 29, 425-433. Au-P, 2.220(9)-2.227(2) Å P-Au-Cl, 172.4(1)-178.8(1)°.
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(a) Attar, S.; Bearden, W. H.; Alcock, N. W.; Alyea, E. C.; Nelson, J. H. Inorg. Chem. 1990, 29, 425-433. Au-P, 2.220(9)-2.227(2) Å P-Au-Cl, 172.4(1)-178.8(1)°.
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114
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(b) Su, H.-C.; Fadhel, O.; Yang, C.-J.; Cho, T.-Y.; Fave, C.; Hissler, M.; Wu, C.-C.; Réau, R. J. Am. Chem. Soc. 2006, 128, 983-995. Au-P, 2.2290(I6)-2.2300(I6) Å P-Au-Cl, 171.64(7)-174.63(8)°.
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38349085940
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Dienes, Y.; Eggenstein, M.; Neumann, T.; Englert, U.; Baumgartner, T. Dalton Trans. 2006, 1424-1433. Au-P, 2.2249(12) Å; P-Au-Cl, 177.26(4)°.
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(c) Dienes, Y.; Eggenstein, M.; Neumann, T.; Englert, U.; Baumgartner, T. Dalton Trans. 2006, 1424-1433. Au-P, 2.2249(12) Å; P-Au-Cl, 177.26(4)°.
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116
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38349105073
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Slow exchange may occur between two coordination states, in which the pyrrole ligands are bound to the palladium non-equivalently
-
Slow exchange may occur between two coordination states, in which the pyrrole ligands are bound to the palladium non-equivalently.
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-
-
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117
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38349163842
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We are planning to perform theoretical study on the oxidative addition of a phenyl halide to P,N2,X-hybrid complexes in detail, to clarify the nature of the active species
-
2,X-hybrid complexes in detail, to clarify the nature of the active species.
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-
-
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118
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23844521950
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Recently, Heyduk and co-workers reported the redox-based bond-making and bond-breaking reactions using a zirconium(IV) redox-active ligand (2,4-di-tert-butyl-6-tert-butylamidophenolate) complex. See: (a) Blackmore, K. J.; Ziller, J. W.; Heyduk, A. F. Inorg. Chem. 2005, 44, 5559-5561.
-
Recently, Heyduk and co-workers reported the redox-based bond-making and bond-breaking reactions using a zirconium(IV) redox-active ligand (2,4-di-tert-butyl-6-tert-butylamidophenolate) complex. See: (a) Blackmore, K. J.; Ziller, J. W.; Heyduk, A. F. Inorg. Chem. 2005, 44, 5559-5561.
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120
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9944245910
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Recent reviews on the nature of the active species in palladium-catalyzed coupling reactions have pointed out that nearly all Pd precatalysts decompose at high temperatures (e.g, > ∼20°C) to liberate soluble ligand-free palladium colloids or nanoparticles. To avoid this uncertainty, the present Heck reactions were conducted at 100°C (a) Beletskaya, I. P, Cheprakov, A. V. J. Organomet. Chem. 2004, 689, 4055-4082
-
Recent reviews on the nature of the active species in palladium-catalyzed coupling reactions have pointed out that nearly all Pd precatalysts decompose at high temperatures (e.g., > ∼20°C) to liberate soluble "ligand-free" palladium colloids or nanoparticles. To avoid this uncertainty, the present Heck reactions were conducted at 100°C (a) Beletskaya, I. P.; Cheprakov, A. V. J. Organomet. Chem. 2004, 689, 4055-4082.
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124
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38349163344
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In our preliminary communication ref 20, we reported the results on the same Heck reaction conducted at 135°C, which gave the turnover number of 9700 after 4 h
-
In our preliminary communication (ref 20), we reported the results on the same Heck reaction conducted at 135°C, which gave the turnover number of 9700 after 4 h.
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125
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4444264948
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For example, see: a
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For example, see: (a) Heck, R. F. Acc. Chem. Res. 1979, 12, 146-151.
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129
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38349121633
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In these reactions, a silyl enol ether was formed as a byproduct, which was converted to the starting substrate, acetophenone, after hydrolysis
-
In these reactions, a silyl enol ether was formed as a byproduct, which was converted to the starting substrate, acetophenone, after hydrolysis.
-
-
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130
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0001276542
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