Coordination complexes and applications of transition metal sulfide and selenide halides

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

“…Although the large soft tellurium centres are not usually thought to be good ligands for high valent d-block metals, a range of compounds has been reported in the last few years, including examples with NbCl 4 , 47 ; complexes of the latter type were reported in the 1970s 7,8 but this is the first structural authentication. The work has provided detailed characterisation of MoOCl 3chalocogenoether complexes, and comparison with the W(VI) and W(V) analogues, and lays the basis for exploration of corresponding molybdenum sulfide chloride complexes, 19 which may provide single source LPCVD reagents for deposition of MoS 2 thin films. The sulfide chloride systems will form the basis of future work.…”

“…18 In contrast, very little data on the molybdenum chalcogenide halides or their coordination complexes exists. 19 The crystal structures of two forms of MoSCl 3 obtained from crystals grown at high temperature found that both contain Mo(IV) as Mo 2 units and disulfide groups, and not Mo(V). 20 It is unclear if MoSCl 3 prepared at low temperatures from MoCl 5 and S(SiMe 3 ) 2 or Sb 2 S 3 contains Mo(V), 21,22 while MoSCl 4 is unknown.…”

“…20 It is unclear if MoSCl 3 prepared at low temperatures from MoCl 5 and S(SiMe 3 ) 2 or Sb 2 S 3 contains Mo(V), 21,22 while MoSCl 4 is unknown. 19 In order to allow comparisons with the WOCl 4 , WOCl 3 , WSCl 4 and WSCl 3 chemistry, we have examined the chemistry of MoOCl 3 with neutral chalcogenoethers and report here complexes of mono-and bi-dentate thio-, seleno-and telluroethers. Data on diphosphine analogues, which clarifies some of the (inconsistent) earlier studies, [7][8][9] is also presented.…”

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

“…[1][2][3] In contrast, the heavier analogues, the sulfide and selenide halides, are little known and have been much less studied. 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.…”

New O‐centered titanium chalcohalide: synthesis and structure of Ti4O(Se2)4Br6

“…Compounds simultaneously consisting of metal, chalcogen and halogen are the family of species interesting from the point of view both diversity of their structures and chemical or physical properties. Indeed, some mononuclear transition metal chalcohalogenides (TMCH) are discussed as volatile precursors for CVD processes; [1] a plenty of cluster complexes with different functionalities (catalysts in hydrorefining of crude oil, X-ray contrast agents, optical limiters) are derived from TMCH compounds of heavy 5-7 group transition metals. [2,3] Unlike transition metals of 5-7 groups, the number of chalcohalide compounds of transition metals of group 4 (Ti, Zr, Hf) is rather limited: to the best of our knowledge, ionic complex [SCl 3 ][Ti 2 Cl 9 ] [4] and Ti 4 Se 9 I 6 [5] are the only ternary TMCH for titanium for to-date.…”