Preparation of trichloride and tetrachloride of molybdenum

Abstract

Molybdenum tr ichloride was successfully prepared in quantity b y the reduction of molybdenum p entachloridc with hydrogen. The most satisfactory yields were obLained with a 4 to 5 mole excess of hydrogen at pressures of 100 psi or higher and at a tem p eratu re of 125°C.Molybdenum tetrachloride "'as prep ared by direct reaction of mol ybde num trichloride with mol ybdenum p entachloride in a sealed tube or steel bomb maintained at 250 0 C. X-ray patterns of the various chlorides were obtained.

Isolation of a Homoleptic Non-oxo Mo(V) Alkoxide Complex: Synthesis, Structure, and Electronic Properties of Penta-tert-Butoxymolybdenum

“…Collectively, these results suggest that alkoxide ligands favor the disproportionation of Mo­(IV), even though a discrete and well-characterized homoleptic Mo­(IV) enolate complex is known that has been made from [MoCl 4 (THF) 2 ] by ligand exchange with the corresponding bulky alkali-metal enolate . [MoCl 4 (THF) 2 ] itself also shows the propensity to disproportionate, although more latently . This complex had previously been recognized as unstable under nitrogen atmosphere, but the decomposition products had not been identified .…”

“… 51 [MoCl 4 (THF) 2 ] itself also shows the propensity to disproportionate, although more latently. 52 This complex had previously been recognized as unstable under nitrogen atmosphere, but the decomposition products had not been identified. 8b When a solution of [MoCl 4 (THF) 2 ] in dichloromethane was kept at ambient temperature for ≥4 d, a solid material started to precipitate that is composed of a 1:1 mixture of the oxo-species 10 , crystallized with one THF and one adventitious water ligand, 53 and the known dinuclear complex 11 ( Scheme 4 ).…”

Technetium Tetrachloride Revisited: A Precursor to Lower-Valent Binary Technetium Chlorides

“…27 Reacting molybdenum metal and excess chlorine yields MoCl 5 . β-MoCl 4 is obtained from the reaction of the pentachloride with MoCl 3 in a sealed tube at 250 °C, 28 while the α phase is synthesized by refluxing MoCl 5 with tetrachloroethylene and carbon tetrachloride. 29 Chlorination of tungsten metal yields WCl 6 , which can then be reduced with aluminum to form the tetrachloride.…”

Phosphorescent Metal Halide Nanoclusters for Tunable Photodynamic Therapy

“…[29] Early on, it was considered to be a trimer; however, the first definite structural characterization was established in 1950 by Vaughan and Pauling in a crystal structure composed of the Mo 6 C1 14 2À ion with MoÀ Mo octahedron surrounded by eight face-bridging and six axial halides. [30][31][32][33][34] Later, in the 1980s, studies using electrogenerated chemiluminescence provided insights for application of inorganic systems in light-emitting devices and electron-transfer reactions in highly exothermic regimes. [35][36][37] More recently, these molecules were used as sensitizers for 1 O 2 generation and oxygen detection in liquids.…”

“…Molybdenum dichloride was first synthesized in 1859 when Blomstrand prepared low‐valence molybdenum halides by passing hydrogen over pentachloride in a hot tube [29] . Early on, it was considered to be a trimer; however, the first definite structural characterization was established in 1950 by Vaughan and Pauling in a crystal structure composed of the Mo 6 C1 14 2− ion with Mo−Mo octahedron surrounded by eight face‐bridging and six axial halides [30–34] . Later, in the 1980s, studies using electrogenerated chemiluminescence provided insights for application of inorganic systems in light‐emitting devices and electron‐transfer reactions in highly exothermic regimes [35–37] .…”