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

Synthesis, properties and structural features of molybdenum(v) oxide trichloride complexes with neutral chalcogenoether ligands

“…[30][31][32] The behaviour contrasts with that of o-C 6 H 4based group 15 ligands, where o-C 6 H 4 (PMe 2 ) 2 or o-C 6 H 4 (AsMe 2 ) 2 can produce seven-or eight-coordination in tungsten(VI) complexes, such as [WOCl 4 {o-C 6 H 4 (PMe 2 ) 2 }] or [WF 4 {o-C 6 H 4 (PMe 2 ) 2 } 2 ] 2+ . 45,46 The present work has also reported the first examples of Mo(V) telluroether complexes.…”

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

“…Similarly, reaction of o-C 6 H 4 (PMe 2 ) 2 with WSeCl 4 in CH 2 Cl 2 instantly produced a green solution and a brown precipitate, and the 31 P{ 1 H} NMR spectrum showed several species present in the solution, with the major resonances at δ = +20 and +33, which may be due to phosphine selenides. This contrasts with the reactions of o-C 6 H 4 (PMe 2 ) 2 with WOCl 4 and WSCl 4 , which gave high yields of the seven-coordinate complexes [WECl 4 {o-C 6 H 4 (PMe 2 ) 2 }] (E = O, S), both of which were characterised, including the X-ray structure of the latter (as noted earlier) 8. Decomposition of [WECl 4 {o-C 6 H 4 (PMe 2 ) 2 }] in CH 2 Cl 2 solution over a few days gave crystals of a number of tungsten(V) species including [WOCl 3 {o-C 6 H 4 (PMe 2 ) 2 }] and [WCl 4 {o-C 6 H 4 (PMe 2 ) 2 } 2 ] + .…”

“…This contrasts with the ready synthesis of WSCl 4 from WCl 6 and S(SiMe 3 ) 2 , and WOCl 4 from WCl 6 and O(SiMe 3 ) 2 . [7][8][9]26 Refluxing WSeCl 4 with Cl 2 CvCCl 2 also failed to produce WSeCl 3 , whereas the similar reaction of WSCl 4 and Cl 2 CvCCl 2 forms WSCl 3 . 27 Green single crystals of WSeCl 4 , which were obtained during the synthesis by sublimation, contained two independent molecules in the asymmetric unit, both monomeric square pyramids, with similar bond lengths and angles (Fig.…”

“…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. 9 Comparisons of the chemistries of TaOCl 3 and TaSCl 3 have also been reported.…”

“…8,35 Rather surprisingly, attempts to isolate the (unknown) anion, [WSeCl 5 ] − with a range of cations, including [PPh 4 ] + and [NEt 4 ] + , have been unsuccessful thus far, whereas the [WSCl 5 ] − and [WS 2 Cl 4 ] 2− ions are well known.…”