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Dioxomolybdenum complexes based on salan ligands have been evaluated for their potential in catalyzing the deoxydehydration (DODH) reaction. The DODH reaction is a formal reduction that converts vicinal diols into... 

Two cis -dioxomolybdenum complexes based on salan ligands with different backbones are reported. The first complex, dioxido{2,2′-[l,2-phenylenebis(iminomethylene)]bis(phenolato)}molybdenum(VI) dimethylformamide disolvate, [Mo(C 20 H 18 N 2 O 2 )O 2 ]·2C 3 H 7 NO ( Ph LMoO 2 , 1b ), features a phenyl backbone, while the second complex, (6,6′-{[(cyclohexane-1,2-diyl)bis(azanediyl)]bis(methylene)}bis(2,4-di- tert -butylphenolato))dioxidomolybdenum(VI) methanol disolvate, [Mo(C 36 H 56 N 2 O 2 )O 2 ]·2CH 3 OH ( Cy LMoO 2 , 2b ), is based on a cyclohexyl backbone. These complexes crystallized as solvated species, 1b ·2DMF and 2b ·2MeOH. The salan ligands Ph LH 2 ( 1a ) and Cy LH 2 ( 2a ) coordinate to the molybdenum center in these complexes 1b and 2b in a κ 2 N ,κ 2 O fashion, forming a distorted octahedral geometry. The Mo—N and Mo—O distances are 2.3475 (16) and 1.9567 (16) Å, respectively, in 1b while the corresponding measurements are Mo—N = 2.3412 (12) Å, and Mo—O = 1.9428 (10) Å for 2b . A key geometrical feature is that the N—Mo—N angle of 72.40 (4)° in Cy LMoO 2 is slightly less than that of the Ph LMoO 2 angle of 75.18 (6)°, which is attributed to the flexibility of the cyclohexane ring between the nitrogen as compared to the rigid phenyl ring in the Ph LMoO 2 .