Bis(2,4-dioxo-pentan-3-ido-κ2 O,O')dioxidomolyb-denum(VI): a redetermination.

Dean H Johnston,Aileen Seitz,Calvin King,Mia Sethi

doi:10.1107/s2414314621007781

Abstract

The title compound, [Mo(C5H7O2)2O2] or cis-[MoO2(acac)2] (acac is acetyl-acetonate), contains a molybdenum(VI) atom coordinated by two acetyl-acetonate ligands and two doubly bonded oxido ligands in a distorted octa-hedral shape. The mol-ecule is chiral and the asymmetric unit contains two independent mol-ecules (one Δ, one Λ). Extensive C-H⋯O contacts are present throughout the structure. Data were collected at 100 K, providing higher precision of unit-cell parameters and atomic positions than previous determinations [Kamenar et al. (1973 ▸). Cryst. Struct. Commun. 2, 41-44.; Krasochka et al. (1975). Zh. Strukt. Khim. 16, 696-698].

Highlights

The title compound, [Mo(C5H7O2)2O2] or cis-[MoO2(acac)2], contains a molybdenum(VI) atom coordinated by two acetylacetonate ligands and two doubly bonded oxido ligands in a distorted octahedral shape
Extensive C—HÁ Á ÁO contacts are present throughout the structure
MoO2(acac)2 has been used to prepare dioxidomolybdenum(VI) complexes with O,N,N0 chelating ligands (Ceylan et al, 2015) and an amine bis(phenolate) ligand (Bowen & Wile, 2021). Many of these complexes have been prepared and studied for their catalytic activities, including complexes with acylpyrazolonate ligands that catalyze the deoxygenation of epoxides (Hills et al, 2013; Begines et al, 2018) and dioxidomolybdenum(VI) complexes with salicylamide ligands for the epoxidation of olefins (Annese et al, 2019)

Summary

Structure description

The title compound is a versatile starting material for the preparation of cis-dioxidomolybdenum complexes, including complexes containing organodinitrogen ligands (Bustos et al, 1994) and molybdenyl adducts of platinum -S dimers (Henderson et al, 2011). MoO2(acac) has been used to prepare dioxidomolybdenum(VI) complexes with O,N,N0 chelating ligands (Ceylan et al, 2015) and an amine bis(phenolate) ligand (Bowen & Wile, 2021). Molybdenum(VI) dioxido complexes with acetylacetonato ligands have been investigated for their catalytic properties in the dehydrogenation of alcohols (Korstanje et al, 2013). These complexes are of particular interest due to their close structural similarities to the active sites of several molybdoenyzmes such as sulfite oxidase, xanthine oxidase, and DMSO reductase (Sousa & Fernandes, 2015).

DÁ Á ÁA

Synthesis and crystallization

Data collection Diffractometer Absorption correction

No of restraints

Data collection

Special details