Structural characterization of MoOCl3(THF)2, the pre-reagent for Kauffmann olefination reactions

Abstract

Single crystals of molybdenum-oxy-di-tetrahydrofuran-trichloride were obtained by the reaction of Mo 2 Cl 10 , tetrahydrofuran, sulfur, and P 4 S 3 in carbon disulfide after layering the solution with n-hexane. Single crystal structure determination at T = 123 K reveals that MoOCl 3 (THF) 2 crystalizes in the orthorhombic space group P2 1 2 1 2 1 with the lattice constants a = 7.8620(9) Å , b = 12.302(1) Å , c = 14.043(2) Å , V = 1304.10(3) Å 3 , and Z = 4. EPR experiments on the solid compound showed a g value of 1.94 at 347.46 mT, which accords to a Mo(V) species. The electronic structure of the title compound was investigated with DFT methods.

Crystal structure and Hirshfeld surface analysis of the elusive trichlorobis(diethyl ether)oxomolybdenum(V)

“…As expected, the O atom of the diethyl ether ligand that is trans to the molybdenum-oxo bond is elongated [2.304 (3) Å ] compared to the O atom trans to a meridional chloro ligand [2.157 3Å ]. In fact, the molybdenum-oxo bond length, as well as the lengths of the meridional chloro ligands, are similar to analogous complexes (Table 3) (Marchetti et al, 2013;Vitzthumecker et al, 2017;Di Nicola et al, 2015). The slight differences in the bond lengths of the meridional chloro ligands can be explained by the donating nature of the coordinating solvents.…”

“…solvent ligands coordinated through the O heteroatoms (Castellani & Gallazzi, 1985;Stoffelbach et al, 2001;Vitzthumecker et al, 2017;Marchetti et al, 2013). Selected bond lengths are shown in Table 2, showcasing the metal-to-ligand bond lengths and angles.…”

“…The ligand represented by 'thf' is tetrahydrofuran. MeO(CH 2 ) 2 OCH 2 Cl] (Marchetti et al, 2013)(Vitzthumecker et al, 2017) (Di Nicola et al, 2015 …”

Isolation of a Homoleptic Non-oxo Mo(V) Alkoxide Complex: Synthesis, Structure, and Electronic Properties of Penta-tert-Butoxymolybdenum

“…In solid form, MoCl 5 is manageable, despite the rather aggressive chemical character that it draws from the combination of strong Lewis acidity, exceptional oxophilicity, and a pronounced oxidizing power; moreover, MoCl 5 is an effective chloride and/or chlorine source. Actually, only few of the commonly used solvents are inert toward MoCl 5 : benzene and related aromatic hydrocarbons succumb to oligomerization and/or chlorination; ethereal solvents face rapid cleavage with concomitant formation of oxo-molybdenum species such as 2 (THF, dioxanes, hexamethyldisiloxane) (Scheme ) and/or serve as single electron reducing agents, entailing the release of Cl 2 (Me 2 O, DME); − acetonitrile also leads to reduction with formation of [MoCl 4 (MeCN) 2 ] and chlorinated acetonitrile byproducts . These examples highlight the vigorous reactivity of MoCl 5 , which can be intentionally used for synthetic purposes, such as the oxidative coupling of (electron-rich) arenes or the formation of esters by catalytic acylative ether cleavage. , …”

A Versatile Comproportionation Route to Construct Mono‐Imido Trichlorido Complexes of Molybdenum(V) and Tungsten(V)

“…[10,11] Notably, these MoÀ N distances in all, A and B as well as 1 and 2 are significantly longer compared to related oxo precursor [MoOCl 3 (L)] (L=THF, MeOCH 2 -CH 2 OCH 2 Cl) (1.6659( 19) and 1.682). [28,29] Since the reaction was found to work well for the aryl-imido complexes, we next turned our interest to the alkyl-imido groups, starting from [Mo(NR) 2 Cl 2 (DME)] (R = t Bu and Ad). Under the same conditions described above, within two hours a color change from yellow-brown to deep blue (3) or blueish-green ( 4) is observed.…”