Journal
DALTON TRANSACTIONS
Volume 39, Issue 28, Pages 6419-6425Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c0dt00064g
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Funding
- MICINN of Spain [CTQ2009-09214, CSD2007-00006]
- Junta de Comunidades de Castilla-La Mancha [PCI08-0032-0957]
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Vanadium oxo-alkoxide complexes [V(O)(Cl)(3-x)(OR)(x)] (x = 1, R = Me (1), Et (2), n-Pr (3); x = 2, R = Me (4), Et (5), n-Pr (6)) were obtained by a clean reaction between [V(O)Cl-3] and different excesses of ROSiMe3 silicon ethers. Imido complexes [V(NAr)(Cl)(3-x)(OR)(x)](2) (Ar = 2,6-i-Pr2C6H3; x = 1, R = Me (7), Et (8), n-Pr (9); x = 2, R = Me (10), Et (11), n-Pr (12)) were prepared in excellent yields by reaction of the oxo-alkoxide precursors and ArNCO. X-Ray crystal structure determinations for 7, 8 and 12 revealed dimeric structures with alkoxide bridges. Complexes 7-12 are precursor of highly active guanylation catalysts. The study of the catalytic reaction allow us to propose the non-participation of the imido moiety. This was confirmed when complexes 1-6 gave better catalysts under the same conditions. The simple and commercial [V(O)Cl-3] (16) can be proposed as the most effective catalyst in this series of vanadium complexes.
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