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

Abstract

First reported in 1930, MoCl3O(Et2O)2 is a by-product of the reductive synthesis of MoCl4(OEt2)2 from MoCl5. We report herein the X-ray crystal structure and Hirshfeld surface characteristics of mer-MoCl3O(Et2O)2, or [MoCl3O(C4H10O)2]. The compound crystallizes in the orthorhombic space group P212121. The molybdenyl (Mo=O) bond length is 1.694 (3) Å and the cis- and trans-Mo—O distances are 2.157 (3) and 2.304 (3) Å, respectively. Intermolecular Mo=O...H bonding is present in the lattice, with the shortest distance being 2.572 Å.

Synthesis, characterization, X-ray and electronic structures of diethyl ether and 1,2-dimethoxyethane adducts of molybdenum(iv) chloride and tungsten(iv) chloride

“…We conducted the reaction at −35 °C instead of the reported −78 °C and obtained the oxo molybdenum( v ) complex, MoOCl 3 (OEt 2 ) 2 , as a minor side product, indicating that strict control of the reaction temperature was unnecessary as comparable yields were obtained. 41 Stoffelbach, Saurenz, and Poli reported a proton NMR spectrum for MoCl 4 (OEt 2 ) 2 in benzene-d 6 , 30 and assigned the ether methyl peak at 1.1 ppm and the methylene peak at 3.5 ppm. These are the free, uncoordinated diethyl ether resonances in benzene-d 6 .…”

“MoCl3(dme)” Revisited: Improved Synthesis, Characterization, and X-ray and Electronic Structures

“…■ RESULTS AND DISCUSSION Synthesis. Because trans-MoCl 4 (Et 2 O) 2 is easy to prepare in high yield directly from commercially available molybdenum pentachloride, 11,12 we chose it as our Mo(IV) starting material, reasoning that (a) it should be soluble in and readily exchange with dme and (b) it could be reduced with a suitable silane. Both of these assumptions proved to be correct.…”