88916-51-2Relevant academic research and scientific papers
Reactions of metal-metal multiple bonds. 10. Reactions of Mo2(OR)6 (M≡M) and [Mo(OR)4]x compounds with molecular oxygen. Preparation and characterization of oxo alkoxides of molybdenum: MoO2(OR)2, MoO2(OR)2(bpy), MoO(OR)4, Mo3O(OR)10, Mo ...
Chisholm, Malcolm H.,Folting, Kirsten,Huffman, John C.,Kirkpatrick, Charles C.
, p. 1021 - 1037 (2008/10/08)
Full title: Reactions of metal-metal multiple bonds. 10. Reactions of Mo2(OR)6 (M≡M) and [Mo(OR)4]x compounds with molecular oxygen. Preparation and characterization of oxo alkoxides of molybdenum: MoO2(OR)2, MoO2(OR)2(bpy), MoO(OR)4, Mo3O(OR)10, Mo4O8(OR)4(py)4, and Mo6O10(OR)12. Mo2(OR)6 (M≡M) compounds and molecular oxygen react in hydrocarbon solvents to give MoO2(OR)2 compounds and alkoxy radicals. For R = t-Bu, the reaction is rapid with no isolable intermediates; for R = i-Pr and CH2-t-Bu, intermediates of formulas Mo3O(OR)10 and Mo6O10(O-i-Pr)12 have been isolated and characterized. [Mo(OR)4]x compounds react with O2 to give MoO(OR)4 compounds where R = t-Bu and x = 1, R = i-Pr and x = 2, and R = CH2-t-Bu and x ≥ 2. Mo(O-t-Bu)4 and O2 also react to yield MoO2(O-t-Bu)2 and t-BuO· in a 1:2 ratio. A general scheme for the reaction of Mo2(OR)6 compounds with O2 is proposed involving an initial facile cleavage of the Mo≡Mo bond to give MoO2(OR)2 and Mo(OR)4 compounds. The subsequent course of the reaction depends on the reactivity of Mo(OR)4 compounds. The new oxo alkoxides MoO2(O-t-Bu)2, MoO2(OR)2(bpy) (where R = i-Pr and CH2-t-Bu), Mo3(μ3-O)(μ3-OR)(μ-OR) 3(OR)6 (where R = i-Pr and CH2-t-Bu), Mo4O8(O-i-Pr)4(py)2, and Mo6O10(O-i-Pr)12 have been characterized by a variety of physicochemical techniques. The oxo groups are formed from the added molecular oxygen. Crystal data: (i) MoO2(O-i-Pr)2(bpy)2·1/2(toluene) at -161°C, a = 13.907 (6) A?, b = 8.413 (3) A?, c = 19.999 (8) A?, α = 111.02 (1)°, β = 71.37 (2)°, γ = 88.98 (1)°, Z = 4, dcalcd = 1.455 g cm-3, space group P1; (ii) Mo3O(OCH2-t-Bu)10·1/3CH 2Cl2 at -161°C, a = 35.557 (19) A?, b = 18.969 (9) A?, c = 19.342 (9) A?, Z = 8, dcalcd = 1.283 g cm-3, space group Pbcn; (iii) Mo3O(O-i-Pr)10 at -162°C, a = 21.274 (6) A?, b = 21.808 (5) A?, c = 10.207 (2) A?, α = 98.69 (1)°, β = 92.92 (1)°, γ = 118.03 (1)°, Z = 4, dcalcd = 1.452 g cm-3, space group P1; (iv) Mo6O10(O-i-Pr)12 at -162°C, a = 13.082 (3) A?, b = 11.478 (2) A?, c = 9.760 (2) A?, α = 106.40 (1)°, β = 91.85 (1)°, γ = 99.81 (1)°, Z = 1, dcalcd = 1.738 g cm-3, space group P1.
