Mohammad Hayatifar, F. Marchetti, G. Pampaloni
Sep 18, 2013
Citations
0
Influential Citations
15
Citations
Journal
Polyhedron
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 3:1 molar reactions of 1 with OCRR′ (R = R′ = Ph; R = H, R′ = 2-C 6 H 4 Me) afforded the complexes Mo(O)Cl 3 (OCRR′) 2 (R = R′ = Ph, 2a ; R = H, R′ = 2-C 6 H 4 Me, 2b ) in high yields. Compound , 3 , was isolated in 35% yield from 1 and 2-acetylfuran. The 1:1 reaction of 1 with phenazine (C 12 H 8 N 2 ) 1 resulted in the formation of MoCl 5 (C 12 H 8 N 2 ), 4 ; the oxydo-chloride derivative Mo(O)Cl 3 [κ 1 ( N )-C 12 H 8 N 2 ], 5 , was prepared straightforwardly by addition of phenazine to Mo(O)Cl 3 , formed in situ upon treatment of 1 with tetrahydrofuran. The addition of a twofold excess of Me 2 NCH 2 CH 2 CO 2 Me to 1 afforded MoCl 4 [κ 1 ( N )-Me 2 NCH 2 CH 2 CO 2 Me] 2 , 6 , in 72% yield. The reaction of 1 with MeO 2 CC CCO 2 Me led to a mixture of inseparable products: MoOCl 3 (κ 1 -MeO 2 CC CCO 2 Me) 2 , 7a , MoCl 5 (κ 1 -MeO 2 CC CCO 2 Me), 7b , and MoCl 4 (κ 1 -MeO 2 CC CCO 2 Me) 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.