Coordination chemistry and applications of medium/high oxidation state metal and non-metal fluoride and oxide-fluoride complexes with neutral donor ligands

Pentagonal bipyramidal complexes of WOCl4 and WSCl4 with diphosphine and diarsine ligands

“…The formation of [WOCl4{o-C6H4(AsMe2)2}] (and the thiochloride analogue) contrasts with the failure of WOF4 to form a complex with the diarsine [19], and probably indicates that WOCl4 is a softer Lewis acid than WOF4. In general, the phosphine complexes with high valent metal-fluoro species in both the d-and p-blocks are significantly more stable than their arsine analogues [24], although we note that both types of ligand form complexes with WF6 [25,26]. Attempts to synthesise complexes of WOCl4 or WSCl4 with PMe3 or AsEt3 under a variety of conditions gave highly impure samples or mixtures including reduction products, hence these were no pursued further.…”

Tungsten(vi) selenide tetrachloride, WSeCl4 – synthesis, properties, coordination complexes and application of [WSeCl4(SenBu2)] for CVD growth of WSe2 thin films

“…4,5 There are no examples of molecular chalcogenide iodides, and whilst chalcogenide fluorides exist for Mo and W, their coordination chemistry is unexplored. 6 The synthesis and chemistry of MEX 3 (M = Nb, Ta; E = S, Se; X = Cl, Br) and WEX 4 were developed in the period 1965-1985, much of it by the groups of Fowles, Rice and Drew. 4,5 We have recently undertaken reinvestigations and comparisons of the coordination chemistry of WSCl 4 and WSCl 3 with those of WOCl 4 and WOCl 3 with a range of N-and O-donor ligands, 7 as well as with the softer phosphines and arsines, 8 and thioethers.…”

Stabilisation of [WF5]+ and WF5 by Pyridine: Facile Access to [WF5(NC5H5)3]+ and WF5(NC5H5)2

“…The WF 5 (NC 5 H 5 ) 2 adduct represents the first heptacoordinate adduct of at ransition-metal pentafluoride;N MR spectroscopic [25,26] and crystallographic [27] studies of MF 5 ·2C 5 H 5 N( M = Nb, Ta )r evealed that MF 5 undergo quantitative ligand-induced autoionisation to the ionic coordination isomers, [MF 4 (NC 5 H 5 ) 4 ] [MF 6 ], upon reactionw ith C 5 H 5 N. Furthermore,t he observation of ionic species upon reactions of MF 5 with excessm onodentate donorl igand,o rs toichiometric amounts of bidentate ligand,i su biquitous. [28,29] Uranium pentafluoride,h owever, forms am onocapped-trigonal-prismatic adduct with 2,2'bipy; [30] UF 5 ·2 HCN insteadm anifests as ao ne-dimensional coordination polymer with trigonal-dodecahedral U V centres. [31] [WF 5 (NC 5 H 5 ) n ] + + (n = 2, 3)…”