662-15-7Relevant academic research and scientific papers
Syntheses of Molybdenum Oxo Benzylidene Complexes
Zhai, Feng,Bukhryakov, Konstantin V.,Schrock, Richard R.,Hoveyda, Amir H.,Tsay, Charlene,Müller, Peter
, p. 13609 - 13613 (2018)
The reaction between Mo(O)(CHAro)(ORF6)2(PMe3) (Aro = ortho-methoxyphenyl, ORF6 = OCMe(CF3)2) and 2 equiv of LiOHMT (OHMT = O-2,6-(2,4,6-Me3C6H2)2C6H3) leads to Mo(O)(CHAro)(OHMT)2, an X-ray structure of which shows it to be a trigonal bipyramidal anti benzylidene complex in which the o-methoxy oxygen is coordinated to the metal trans to the apical oxo ligand. Addition of 1 equiv of water (in THF) to the benzylidyne complex, Mo(CArp)(OR)3(THF)2 (Arp = para-methoxyphenyl, OR = ORF6 or OC(CF3)3 (ORF9)) leads to formation of {Mo(CArp)(OR)2(μ-OH)(THF)}2(μ-THF) complexes. Addition of 1 equiv of a phosphine (L) to Mo(CArp)(ORF9)3(THF)2 in THF, followed by addition of 1 equiv of water, all at room temperature, yields Mo(O)(CHArp)(ORF9)2(L) complexes in good yields for several phosphines (e.g., PMe2Ph (69% by NMR), PMePh2 (59%), PEt3 (69%), or P(i-Pr)3 (65%)). The reaction between Mo(O)(CHArp)(ORF9)2(PEt3) and 2 equiv of LiOHMT proceeds smoothly at 90 °C in toluene to give Mo(O)(CHArp)(OHMT)2, a four-coordinate syn alkylidene complex. Mo(O)(CHArp)(OHMT)2 reacts with ethylene (1 atm in C6D6) to give (in solution) a mixture of Mo(O)(CHArp)(OHMT)2, Mo(O)(CH2)(OHMT)2, and an unsubstituted square pyramidal metallacyclobutane complex, Mo(O)(CH2CH2CH2)(OHMT)2, along with ethylene and ArpCH=CH2. Mo(O)(CHArp)(OHMT)2 also reacts with 2,3-dicarbomethoxynorbornadiene to yield syn and anti isomers of the "first-insertion" products that contain a cis C=C bond.
Synthesis of Ether-Functionalized and Sterically Demanding Molybdenum Alkylidyne Complexes
àrias, òscar,Ehrhorn, Henrike,H?rdter, Johanna,Jones, Peter G.,Tamm, Matthias
supporting information, p. 4784 - 4800 (2019/01/04)
The synthesis of ether-functionalized molybdenum benzylidyne complexes [ArC-Mo{OC(CF3)2Me}3] (6, Ar = para-methoxyphenyl; 7, Ar = 2,4,6-trimethoxyphenyl) and of the sterically demanding benzylidyne complex [{2,4,6-(i-Pr)3C6H2}C-Mo{OC(CF3)2Me}3] are presented, together with their spectroscopic characterization, molecular structures, and catalytic activity in alkyne metathesis. Complexes 6 and 7 feature intermolecular contacts between the para-methoxy group and the molybdenum center that give rise to 1D-polymeric structures in the solid state. The preparation of other functionalized alkylidyne complexes, [ArC-Mo{OC(CF3)2Me}3] (Ar = 2-(i-PrO)C6H4, 8-MeO-Naph, 2,6-(i-Pr)2C6H3), was also attempted, but only the acyl precursors [ArC(=O)Mo(CO)5]- could be isolated. The synthesis of the molybdenum acyl complexes was challenging, and appropriate alternative protocols were developed.
METHOD FOR PRODUCING 1,1,1,3,3,3-HEXAFLUORO-tert-BUTANOL
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Paragraph 0052, (2016/10/07)
PROBLEM TO BE SOLVED: To provide an efficient method for producing 1,1,1,3,3,3-hexafluoro-tert-butanol (abbreviation: HFTB). SOLUTION: The method for producing HFTB at least comprises a first step to a third step. The first step: a step of contacting a first mixture at least containing HFTB and one or more ether type solvent selected from the group consisting of diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, diethoxymethane, and dimethoxymethane with an alkali metal base to obtain a second mixture at least containing an alkali metal 1,1,1,3,3,3-hexafluoro-tert-butoxide and the ether solvent. The second step: a step of separating the ether type solvent from the second mixture obtained in the first step. The third step: a step of obtaining HFTB by contacting the second mixture after the second step with an acid. COPYRIGHT: (C)2016,JPOandINPIT
K×××F/O interactions bridge copper(I) fluorinated alkoxide complexes and facilitate dioxygen activation
Lum, June S.,Tahsini, Laleh,Golen, James A.,Moore, Curtis,Rheingold, Arnold L.,Doerrer, Linda H.
, p. 6374 - 6384 (2013/08/15)
Seven E[Cu(OR)2] copper(I) complexes (E=K+, {K(18C6)}+ (18C6=[18]crown-6), or Ph4P+; R=C4F9, CPhMeF2, and CMeMe F2) have been prepared and their reactivity with O 2 studied. The K[Cu(OR)2] species react with O2 in a copper-concentration-dependent manner such that 2:1 and 3:1 Cu/O 2 adducts are observed manometrically at -78 °C. Analogous reactivity with O2 is not observed with the {K(18C6)}+ or Ph4P+ derivatives. Solution conductivity data demonstrate that these K[Cu(OR)2] complexes do not behave as 1:1 electrolytes in solution. The K+ ions induce aggregation of multiple [Cu(OR) 2]- units through K×××F/O interactions and thereby effect irreversible O2 reduction by multiple Cu centers. Bond valence analyses for the potassium cations confirm the dominance of the fluorine interactions in the coordination spheres of K+ ions. Intramolecular hydroxylation of ligand aryl and alkyl C-H bonds is observed. Nucleophilic reactivity with CO2 is observed for the oxygenated Cu complexes and a CuII carbonate has been isolated and characterized. Copyright
