Synthesis and Investigations of the Crystal Structure of aDinuclear Diazadiene Molybdenum Oxo‐Imido Complex with a Unique N₃Mo(μ‐O)₂MoN₃ Core

Abstract

Ligand metathesis of the diimido and dioxo precursor complexes [Mo(X)2Cl2(DME)] (X = O, NtBu) leads to the mixed oxo‐imido derivative [Mo(NtBu)(O)Cl2(DME)] (1). By treatment with Li2DAD (DAD = 1,4‐di‐tert‐butyl‐1,4‐diazabuta‐1,3‐diene), 1 is converted into the complex [Mo(NtBu)(O)(DAD)]2 (2). The crystal structure determination on a nonmerohedral twin of 2 reveals a dinuclear molecular structure with nearly symmetrical bridging oxygen atoms. The smaller oxo ligand tends to be a better bridging functionality than the imido ligand; the unprecedented N3Mo(μ‐O)2MoN3 configuration is favored over a ON2Mo(μ‐N)2MoN2O core. Compared to other known molybdenum DAD complexes, 2 reveals some degree of pyramidalization at the nitrogen atoms of the DAD ligand. In accord with the Mo–N, N–C, and C–C bond lengths, complex 2 is best described as an ene‐diamido complex of formally six‐valent molybdenum. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Bioinspired functional analogs of the active site of molybdenum enzymes: Intermediates and mechanisms

“…Functionalization of the Schiff base chelate ligands HL to modulate the molybdenum complex properties. [88,89], HL 3 and NEt 3 (Scheme 6, Eq. (2)) [82].…”

Stereochemical Consequences of Oxygen Atom Transfer and Electron Transfer in Imido/Oxido Molybdenum(IV, V, VI) Complexes with Two Unsymmetric Bidentate Ligands

“…After heating to reflux for 3 h the suspension was filtered, and the red filtrate was dried under reduced pressure. The 20,23 (1.0 g, 2.9 mmol) was dissolved in THF (50 mL), and the deprotonated ligand was added. After heating to reflux for 7 h the suspension was filtered, and the red filtrate was dried under reduced pressure (95% raw yield).…”

Activation of Molecular Oxygen by a Molybdenum(IV) Imido Compound

“…The oxido imido complexes [MoO(NtBu)(L)2], 1a and 1b, were prepared by reacting [MoO(NtBu)Cl2(dme)] [22][23][24] with the respective iminophenolate ligands HL1 25 (R= Me) or HL2 (R= tBu), 26 as shown in Scheme 1.…”