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Related reviews for olefm polymerization catalysts (including vanadium complexes): (a) Gambarotta, S. Coord. Chem. Rev. 2003, 237, 229.
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Pioneering examples: (a) Carrick, W. L. J. Am. Chem. Soc. 1958, 80, 6455.
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Pioneering examples for synthesis of block copolymers by living polymerization using vanadium catalysts: (a) Doi, Y.; Ueki, S.; Soga, K. Macromolecules 1979, 12, 814.
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Examples for structurally characterized V(V) alkyls: (a) de With, J.; Horton, A. D.; Orpen, A. G. Organometallics 1990, 9, 2207.
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Our previous examples: (a) Yamada, J, Fujiki, M, Nomura, K. Organometallics 2005, 24, 2248
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Our previous examples: (a) Yamada, J.; Fujiki, M.; Nomura, K. Organometallics 2005, 24, 2248.
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Related review article: (a) Copéret, C.; Chavanas, M.; Saint-Arroman, R. P.; Basset, J. M. Angew. Chem., Int. Ed. 2003, 42, 156.
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(b) Thomas, J. M.; Raja, R.; Lewis, D. W. Angew. Chem., Int. Ed. 2005, 44, 6456.
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Recent examples: (a) Rhers, B.; Salameh, A.; Baudouin, A.; Quadrelli, E. A.; Taoufik, M.; Copéret, C.; Lefebvre, F.; Basset, J. -M.; Solans-Monfort, X.; Eisenstein, O.; Lukens, W. W.; Lopez, L. P. H.; Sinha, A.; Schrock, R. R. Organometallics 2006, 25, 3554.
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Recent examples: (a) Rhers, B.; Salameh, A.; Baudouin, A.; Quadrelli, E. A.; Taoufik, M.; Copéret, C.; Lefebvre, F.; Basset, J. -M.; Solans-Monfort, X.; Eisenstein, O.; Lukens, W. W.; Lopez, L. P. H.; Sinha, A.; Schrock, R. R. Organometallics 2006, 25, 3554.
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Marks, T.J.3
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For more details, see the Supporting Information
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For more details, see the Supporting Information.
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47
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0001119496
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Selected related examples for synthesis of Ti(IV) or Zr(IV) alkoxide-alkene complexes: (a) Wu, Z.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1995, 117, 5867.
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Selected related examples for synthesis of Ti(IV) or Zr(IV) alkoxide-alkene complexes: (a) Wu, Z.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1995, 117, 5867.
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48
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(b) Carpentier, J. F.; Wu, Z.; Lee, C. W.; Strömberg, S.; Christopher, J. N.; Jordan, R. F. J. Am. Chem. Soc. 2000, 122, 7750.
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Synthesis and structural determination of Cp*TiMe[OCH 2(CH2)n-CH=CH2](O-2,6- iPr2C6H3, n, 1, 3) and Cp*Ti(CF3SO3)[OCH2(CH2) n-CH=CH2]O-2,6-iPr2C 6H3, Nomura, K, Hatanaka, Y. Inorg. Chem. Commun. 2003, 6, 517
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3): Nomura, K.; Hatanaka, Y. Inorg. Chem. Commun. 2003, 6, 517.
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A reviewer pointed out a possibility of formation of the [2+2] adduct with the arylimido complex as proposed by Odom et al. for synthesis of amines by titanium-mediated transfer of alkenyl groups from alcohol Ramanathan, B.; Odom, A. L. J. Am. Chem. Soc. 2006, 128, 9344.
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A reviewer pointed out a possibility of formation of the [2+2] adduct with the arylimido complex as proposed by Odom et al. for synthesis of amines by titanium-mediated transfer of alkenyl groups from alcohol (Ramanathan, B.; Odom, A. L. J. Am. Chem. Soc. 2006, 128, 9344.
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Related report for hydroamination of alkynes by (arylimido) vanadium complexes: Lorber, C.; Choukroun, R.; Vendier, L. Organometallics 2004, 23, 1845).
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Related report for hydroamination of alkynes by (arylimido) vanadium complexes: Lorber, C.; Choukroun, R.; Vendier, L. Organometallics 2004, 23, 1845).
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1H NMR spectra, and the observed equilibrium is reversible. In addition, no resonances ascribed to the carbene species were seen. On the basis of these results, it is concluded that the formed species are simple olefin-coordinated species, although we could not completely exclude a possibility of formation of the metallacycle. For example (tungsten, titanium): (a) Bennett, J.; Wolczanski, P. T. J. Am. Chem. Soc. 1997, 119, 10696.
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1H NMR spectra, and the observed equilibrium is reversible. In addition, no resonances ascribed to the carbene species were seen. On the basis of these results, it is concluded that the formed species are simple olefin-coordinated species, although we could not completely exclude a possibility of formation of the metallacycle. For example (tungsten, titanium): (a) Bennett, J.; Wolczanski, P. T. J. Am. Chem. Soc. 1997, 119, 10696.
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Lokare, K. S.; Ciszewski, J. T.; Odom, A. L. Organometallics 2004, 23, 5386. K.N. expresses his thanks to a reviewer for pointing out this issue.
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(b) Lokare, K. S.; Ciszewski, J. T.; Odom, A. L. Organometallics 2004, 23, 5386. K.N. expresses his thanks to a reviewer for pointing out this issue.
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Although the exclusive formation of Sa could be confirmed by both 1H and 51V NMR spectra, an attempt to isolate 5a as microcrystals was unsuccessful probably due to the improved solubility in organic solvent and/or contamination of residual phenol in trace amounts. The identification of 5a was thus made by comparison of both 1H and 51V NMR spectra with the chloro-bis(aryloxo) analogue, ArN)VCl(0-2,6-Me2C6H3)2 (6, and the tris(aryloxo) analogue, ArN)V(O-2,6-Me2C6H 3)3 (7, which could be prepared and identified independently by the reaction of (ArN)VCl3 with 2.0 or 3.0 equiv of LiO-2,6-Me2C6H3 Et2O according to the analogous method for the preparation of (ArN)VCl2(O-2,6-Me 2C6H3).22
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The result for simple energy evaluations [coordination energies defined as ΔEcoord, E(complex1, E (2,6-Me2C6H3OH, E(proposed intermediate, E (complex 1, E(2,6-Me2C6H3OH, E (proposed intermediate) are heat of formation for complex 1, 2,6-Me2C6H3OH, and the proposed intermediates, respectively] for three proposed intermediates in the reaction [equilibrium geometry at ground state with semiempirical PM3, geometry optimization, RHF/PM3D Spartan '04 for Windows (Wavefunction Inc, suggested that co-ordination of phenol trans to the methyl group seemed more stable (ΔEcoord, 3.31 kcal/mol) than the others [ΔEcoord, 1.97 and -24.88 kcal/mol for the proposed intermediates when the phenol coordinates trans to arylimido and ketimide, respectively, In contrast, the coordination of 2,6-Me2C6H3SH to the van
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3SH trans to arylimido, ketimide, and Me, respectively). These results may also suggest the formation of five-coordinated trigonal bipyramidal species by coordination of the phenol to 1, although more precise geometry optimizations are necessary for a more precise evaluation.
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A reviewer commented that we do not mention the possibility of the arylimido ligand acting as a proton shuttle. As described in ref 25 and our experimental results, the reaction of 1 with thiols may occur by simple protonolysis not by coordination of thiols, although we do not have clear evidence for the mechanism
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A reviewer commented that we do not mention the possibility of the arylimido ligand acting as a proton shuttle. As described in ref 25 and our experimental results, the reaction of 1 with thiols may occur by simple protonolysis not by coordination of thiols, although we do not have clear evidence for the mechanism.
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