title: Salt-free reducing reagent of bis(trimethylsilyl)cyclohexadiene mediates multielectron reduction of chloride complexes of W(VI) and W(IV).
abstract: We developed a salt-free reduction of WCl6 using 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene (MBTCD) in toluene to give a low-valent trinulcear tungsten complex involving W(II) and W(III) centers, while in the presence of redox active ligands such as α-diketone and α-diimine the same reduction produced W(IV) complexes with the corresponding redox-active ligands, (α-diketone)WCl4 and (α-diimine)WCl4. A W(VI) complex with two α-diketone ligands, (α-diketone)2WCl2, was found to be synthetically equivalent to low-valent W(IV) species that trapped azopyridine to give (α-diketone)WCl2(azopyridine).
authors.affiliation: Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan.
authors.forename: Hayato
authors.initials: H
authors.lastname: Tsurugi
authors.forename: Hiromasa
authors.initials: H
authors.lastname: Tanahashi
authors.forename: Haruka
authors.initials: H
authors.lastname: Nishiyama
authors.forename: Waldemar
authors.initials: W
authors.lastname: Fegler
authors.forename: Teruhiko
authors.initials: T
authors.lastname: Saito
authors.forename: Andreas
authors.initials: A
authors.lastname: Sauer
authors.forename: Jun
authors.initials: J
authors.lastname: Okuda
authors.forename: Kazushi
authors.initials: K
authors.lastname: Mashima