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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]

Abstract: The interactions of molybdenum pentachloride (1) with a variety of organic compounds were studied in dichloromethane and the metal products were isolated in the solid state. The 3:1molar reactions of 1 with OCRR′ (R=R′=Ph; R=H, R′=2-C6H4Me) afforded the complexes Mo(O)Cl3(OCRR′)2 (R=R′=Ph, 2a; R=H, R′=2-C6H4Me, 2b) in high yields. Compound ▪, 3, was isolated in 35% yield from 1 and 2-acetylfuran. The 1:1 reaction of 1 with phenazine (C12H8N2) 1 resulted in the formation of MoCl5(C12H8N2), 4; the oxydo-chloride derivative Mo(O)Cl3[κ1(N)-C12H8N2], 5, was prepared straightforwardly by addition of phenazine to Mo(O)Cl3, formed in situ upon treatment of 1 with tetrahydrofuran. The addition of a twofold excess of Me2NCH2CH2CO2Me to 1 afforded MoCl4[κ1(N)-Me2NCH2CH2CO2Me]2, 6, in 72% yield. The reaction of 1 with MeO2CC CCO2Me led to a mixture of inseparable products: MoOCl3(κ1-MeO2CC CCO2Me)2, 7a, MoCl5(κ1-MeO2CC CCO2Me), 7b, and MoCl4(κ1-MeO2CC CCO2Me)2, 7c, were recognized by combined EPR/DFT investigation. Analogous DFT/EPR studies were performed on 2b and 4. The X-ray structures of 2a, 3 and 5 were determined; the X-ray structure of 5 represents a rare example of crystallographically-characterized pentacoordinated Mo(V) neutral complex. [Copyright &y& Elsevier]

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]