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Oxido-molybdenum complexes obtained by Cl/O interchange between MoCl5 and carboxylic acids: a crystallographic, spectroscopic and computational study.
- Source :
-
Dalton Transactions: An International Journal of Inorganic Chemistry . 2014, Vol. 43 Issue 43, p16416-16423. 8p. - Publication Year :
- 2014
-
Abstract
- The direct interaction of MoCl5 with a series of carboxylic acids has been elucidated for the first time. The reactions proceed with release of hydrogen chloride and Cl/O interchange between the metal centre and one equivalent of organic substrate: this feature is unique in the context of the chemistry generally shown by transition metal halides with carboxylic acids. The dinuclear complexes [MoOCl2(¹-CX3CO2H)(µ-Cl)]2 (X = H, 1a; X = Cl, 1b) and Mo2O2Cl6(μ-CH3CO2H), 2a, were isolated as the prevalent metal products of the 1 : 2 molar reactions of MoCl5 with CH3COOH and CCl3COOH. Evidence for the formation of Mo2O2Cl6(μ-CCl3CO2H), 2b, was achieved by allowing MoCl5 to react with CCl3COOH in 2 : 3 ratio. Instead the reactions of MoCl5 with a three-fold molar excess of RCOOH afforded the mononuclear complexes MoOCl3(¹-RCO2H)2 (R = CH3, 3a; CCl3, 3b; CHCl2, 3c; CMe3, 3d) in 50-60% yields. The new compounds were characterized by analytical and spectroscopic techniques, moreover the X-ray molecular structures were ascertained for 1a, 1b and 2a; 1a and 1b display single Mo-Mo bond. DFT calculations were carried out in order to shed light into structural aspects. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14779226
- Volume :
- 43
- Issue :
- 43
- Database :
- Academic Search Index
- Journal :
- Dalton Transactions: An International Journal of Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 100113083
- Full Text :
- https://doi.org/10.1039/c4dt02201g