1. Different outcomes in the reactions of WCl6 with carboxylic acids.
- Author
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Bortoluzzi, Marco, Guarra, Federica, Marchetti, Fabio, Pampaloni, Guido, and Zacchini, Stefano
- Subjects
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CARBOXYLIC acids , *HEALTH outcome assessment , *CHEMICAL reactions , *DICHLOROMETHANE , *REACTION mechanisms (Chemistry) , *PYRIDINE - Abstract
The reactions of WCl 6 with a selection of carboxylic acids were investigated by using dichloromethane as reaction medium. The addition of pyridine-3-carboxylic acid (niacin) to WCl 6 gave [C 5 H 4 NHC(O)Cl][WOCl 5 ], 1 , in 75% yield via selective Cl/O interchange. WCl 6 reacted with RCO 2 H (R = CH 3 , CBr 3 , CHCl 2 ) in 1:2 ratio resulting in the formation of HCl and the respective acyl chlorides, RC(O)Cl. WOCl 4 (κ 1 -CH 3 CO 2 H), 2 , was isolated from WCl 6 /CH 3 CO 2 H in 41% yield. The 1:2 reaction of WCl 6 with CCl 3 CO 2 H proceeded with HCl release affording a mixture of WCl 5 (O 2 CCCl 3 ), 3 , and WCl 4 (O 2 CCCl 3 ) 2 , 4 . Compound 3 was isolated from WCl 6 /CCl 3 CO 2 H (1:1 ratio) in 60% yield. All the metal products were characterized by analytical and spectroscopic techniques. The crystal structure of 1 was ascertained by X-ray diffractometry. DFT calculations were carried out in order to shed light into structural, mechanistic and thermodynamic features. [ABSTRACT FROM AUTHOR]
- Published
- 2015
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