Interactions of [Mo(Co)6] and [Mo(CO)3(C6H5CH3)] with O2N2– and O2N3-donor macrocycles and the X-ray crystal structure of tetracarbonyl(6,7,16,17-tetrahydro-15H-dibenzo[e,n][1,4,8,12]dioxadiazacyclopentadecine)-molybdenum–toluene (2/1)

Abstract

The reaction of [Mo(CO)₆] with the macrocyclic ligand 6,7,16,17-tetrahydro-15H dibenzo[e,n][1,4,8,12]dioxadiazacyclopentadecine (L¹) in n-octane, gives [Mo(CO)₄L¹]. The crystal and molecular structure of [ Mo(CO)₄L¹]·5C₆H₅CH₃ has been solved by X-ray diffraction methods. It is a monomer with Mo⁰ co-ordinated to four carbon monoxide molecules and two iminonitrogens in a pseudo-octahedral geometry; crystals are monoclinic, space group P2₁/c, with a= 15.625(4), b= 11.554(3), c= 14.590(3)Å, β= 109.01(2)°, and Z= 4. Final R= 0.065 for 933 observed reflections. The reaction of [Mo(CO)₃(C₆H₅CH₃)] with L¹ in methanol gives the orange-red crystalline complex [{Mo(CO)₃L¹}_x](2). By reacting the complex [Mo(CO)₃(C₆H₅CH₃)] with N,N-bis(3-aminopropyl)methylamine and 2,2′-(ethylenedioxy)dibenzaldehyde (1:1:1 ratio), in toluene, the complex [Mo(CO)₃L²](5)(L²= 6,7,16,17,20,21 -hexahydro-15H, 19H-18-methyl-dibenzo[e,r][1,4,8,12,16]dioxatriazacyclononadecine) was obtained as an orange-red microcrystalline solid. Complexes (2) and (5) have been analytically and spectroscopically characterized.