Abstract
Two cis-dioxomolybdenum complexes based on salan ligands with different backbones are reported. The first complex, dioxido{2,2'-[l,2-phenyl-enebis(imino-methyl-ene)]bis-(phenolato)}molybdenum(VI) di-methyl-formamide disolvate, [Mo(C20H18N2O2)O2]·2C3H7NO (PhLMoO2, 1b), features a phenyl backbone, while the second complex, (6,6'-{[(cyclo-hexane-1,2-di-yl)bis(aza-nedi-yl)]bis-(methyl-ene)}bis-(2,4-di-tert-butyl-phenolato))dioxidomolybdenum(VI) methanol disolvate, [Mo(C36H56N2O2)O2]·2CH3OH (CyLMoO2, 2b), is based on a cyclo-hexyl backbone. These complexes crystallized as solvated species, 1b·2DMF and 2b·2MeOH. The salan ligands PhLH2 (1a) and CyLH2 (2a) coordinate to the molybdenum center in these complexes 1b and 2b in a κ2 N,κ2 O fashion, forming a distorted octa-hedral 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 CyLMoO2 is slightly less than that of the PhLMoO2 angle of 75.18 (6)°, which is attributed to the flexibility of the cyclo-hexane ring between the nitro-gen as compared to the rigid phenyl ring in the PhLMoO2.
Highlights
Chemical contextMolybdenum centers are present in the active sites of various enzymes including nitrogenases, sulfite oxidase, xanthine oxidase, and DMSO reductase that catalyze two-electron redox processes (Hille et al, 2014; Enemark et al, 2004; Hille, 1996)
Two cis-dioxomolybdenum complexes based on salan ligands with different backbones are reported
A key geometrical feature is that the N—Mo—N angle of 72.40 (4) in CyLMoO2 is slightly less than that of the PhLMoO2 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 PhLMoO2
Summary
Molybdenum centers are present in the active sites of various enzymes including nitrogenases, sulfite oxidase, xanthine oxidase, and DMSO reductase that catalyze two-electron redox processes (Hille et al, 2014; Enemark et al, 2004; Hille, 1996). This is attributed to the large number of stable oxidation states and coordination environments that can be achieved, as well as the solubility of molybdate salts in water. The second is a known complex with a new unit cell, (Ziegler et al, 2009), 6,60{[(cyclohexane-1,2-diyl)bis(azanediyl)]bis(methylene)}bis(2,4di-tert-butylphenolato))dioxidomolybdenum(VI), CyLMoO2 (2b)
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