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

The bis(diethyl ether) and 1,2-dimethoxyethane (dme) adducts of molybdenum(IV) chloride and tungsten(IV) chloride are valuable starting materials for a variety of synthetic inorganic and organometallic reactions. Despite the broad utility and extensive use of these 6-coordinate complexes, their syntheses remain unoptimized, and their characterization incomplete after more than three decades. While exploring the ligand exchange behaviour of trans -MoCl 4 (OEt 2 ) 2 , we obtained single crystals of this red-orange complex and subsequently compared its structural parameters with those of the recently reported trans -WCl 4 (OEt 2 ) 2 . Significantly improved procedures for both MoCl 4 (dme) and WCl 4 (dme) were developed, and X-ray diffraction data were obtained and analysed. The magnetic properties of the dme adducts were probed, both with Gouy and SQUID magnetometry measurements. The magnetic moment of WCl 4 (dme) was smaller than that of MoCl 4 (dme), an observation that we attribute to the greater spin-orbit coupling of tungsten. Electronic structure studies were also conducted to probe the preferential trans configuration of the diethyl ether adducts and to assign the UV-Vis spectra of the dme adducts.