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Volumn 26, Issue 10, 2007, Pages 2579-2588

Synthesis of various (arylimido)vanadium(V)-methyl complexes containing ketimide ligands and reactions with alcohols, thiols, and borates: Implications for unique reactivity toward alcohols

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; ALCOHOLS; COMPLEXATION; OXYGEN; PHENOLS; SYNTHESIS (CHEMICAL); TEMPERATURE DISTRIBUTION;

EID: 34249005854     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om061121w     Document Type: Article
Times cited : (27)

References (81)
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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
    • 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
    • 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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