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The 1:1 M reaction of MoCl 5 with Cl(CH 2 ) 2 OH, in dichloromethane at room temperature, proceeded with chlorine–oxygen interchange and HCl release to give MoOCl 3 in 65% yield. The analogous reactions involving i PrOH, MeOH, L -menthol and H 2 O gave impure MoOCl 3 . MoCl 5 reacted with Me 2 N(CH 2 ) 2 OH in 1:1 M ratio affording the 2-chloroammonium salt [Me 2 NH(CH 2 ) 2 Cl] 2 [Mo 2 O 2 Cl 8 ], 1 . The reaction of MoCl 5 with MeO(CH 2 ) 2 OH afforded a mixture of [Mo(κ 2 O , O ′-O(CH 2 ) 2 OMe) 2 Cl 2 ][Mo 2 O 2 Cl 7 ], 2a , and [Mo(κ 2 O , O ′-O(CH 2 ) 2 OMe) 2 Cl 2 ][MoOCl 4 ], 2b . The products 1 , 2a and 2b were characterized by analytical and spectroscopic techniques, and by X-ray diffractometry. The X-ray structure of 2b shows weak anion–anion interactions, therefore 2b might be alternatively viewed as a Mo 2 O 2 Cl 8 2− salt. [ABSTRACT FROM AUTHOR]

The mononuclear complexes MoCl 5 L (L = 2,5-dihydrothiophene-1,1-dioxide), 1 , and MoCl 4 L 2 (L = dimethylsulfone, 2 ; diethylsulfone, 3 ; diphenylsulfone, 4 ) were obtained by the reactions of MoCl 5 with the corresponding sulfones at room temperature in dichloromethane, and were characterized by analytical and magnetic data, and by X-ray crystallography in the cases of 1 and 2 . The X-ray structure of 1 is the first one ever reported for an adduct of MoCl 5 with a carbon-containing species. [ABSTRACT FROM AUTHOR]

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]