Molybdenum Oxide Trichloride

Larson, Melvin L.; Moore, Fred W.; Edwards, D. A.

doi:10.1002/9780470132432.ch33

Cited by 2 publications

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“…A much higher yield of 89% was obtained with MoOCl 3 as starting material. This molybdenum precursor gave 2b in 73% yield as a purple solid . The HR EI mass spectra show prominent peaks at m / z 649.15 ( 2a ) and 565.053 ( 2b ), which can be assigned to the cations [(OSSO)MoOCl] + .…”

Section: Resultsmentioning

confidence: 99%

“…Mono(oxo) molybdenum(V) complexes [(OSSO)MoOCl] ( 2a , b ) were prepared by salt metathesis of (MOC 6 H 2 -R 1 -4-R 2 -6) 2 {S(CH 2 ) 2 S} (R 1 = R 2 = t Bu for 2a ; R 1 = Me, R 2 = t Bu for 2b ; M = Li, K) with MoOCl 4 or with MoOCl 3 (Scheme ). When MoOCl 4 was used, the reaction was selective only in toluene. Monitoring the reaction of MoOCl 4 with [(OSSO)Li 2 ] in [D 8 ]toluene showed the formation of a C 2 -symmetric intermediate A , which was subsequently reduced to the paramagnetic Mo(V) complex 2 .…”

Section: Resultsmentioning

confidence: 99%

“…This molybdenum precursor gave 2b in 73% yield as a purple solid. 15 The HR EI mass spectra show prominent peaks at m/z 649.15 (2a) and 565.053 (2b), which can be assigned to the cations [(OSSO)MoOCl] + . The elemental composition could not be determined by combustion analysis, most likely due to contamination with metal halide salts and carbide formation.…”

Section: ■ Introductionmentioning

confidence: 99%

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Oxygen Atom Transfer Reactions with Molybdenum Cofactor Model Complexes That Contain a Tetradentate OSSO-Type Bis(phenolato) Ligand

et al. 2018

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The catalytic activity of molybdenum complexes in oxidation state +IV, +V, and +VI stabilized by a tetradentate dithiaalkanediyl-2,2′-bis(phenolato) (OSSO)-type ligand was tested in the oxygen atom transfer (OAT) reaction from DMSO to PPh 3 . The molybdenum(IV) complexes [(OSSO)MoCl 2 ] (1a, b) were prepared from [MoCl 4 (NCMe) 2 ] and the corresponding bis(phenol) (OSSO)H 2 . The molybdenum(V) complexes [(OSSO)MoOCl] (2a, b) were obtained by salt metathesis either from MoOCl 4 or from MoOCl 3 with the corresponding bis(phenolate) salts [(OSSO)M 2 ] (M = Li, K). The reaction with MoOCl 4 proceeds via the intermediate [(OSSO)MoOCl 2 ] (A), which disproportionates into 2 and insoluble oligomers. Single crystal X-ray diffraction of 1a and 2b revealed octahedral cis-α-coordination of the metal center. EPR spectra of 2a and 2b show the characteristic signal of a molybdenum d 1 -spin system which is not coupled to the ligand. OAT reactions in the presence of 1−2 or of the bis(oxo) complex [(OSSO)MoO 2 ] (3) revealed that the molybdenum(IV) complex 1b exerts the high catalytic activity with complete conversion of PPh 3 to OPPh 3 within 30 min at 60 °C. The high catalytic activity of 1 compared to that of 2−3 is explained by the formation of the unstable intermediate A, which decomposes to 2 in the absence of PPh 3 .

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Oxygen Atom Transfer Reactions with Molybdenum Cofactor Model Complexes That Contain a Tetradentate OSSO-Type Bis(phenolato) Ligand

et al. 2018

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“…MoF 3 , MoF 4 , MoF 5 and MoF 6 [1][2][3][4], but only MoF 6 has commercial applications, primarily in the electronics industry [5]. Usually the volatile, hygroscopic molybdenum hexafluoride (MoF 6 ) is formed by reacting molybdenum metal with strong fluorinating agents, such as F 2 , BrF 3 , and SF 6 [6].…”

Section: Introductionmentioning

confidence: 99%

“…In most cases the lower molybdenum fluorides (MoF 3 , MoF 4 , and MoF 5 ) are formed through the reduction of high oxidation state metal fluorides [7].…”

Section: Introductionmentioning

confidence: 99%