544-97-8Relevant articles and documents
Dong et al.
, p. L225 (1978)
Dunlop,Price
, p. 3205,3206 (1970)
Long,Cattanach
, p. 340 (1961)
Selective oxidation of the alkyl ligand in rhenium(V) oxo complexes
DuMez, Darin D.,Mayer, James M.
, p. 12416 - 12423 (1996)
Rhenium(V) oxo alkyl triflate compounds (HBpz3)ReO(R)OTf [R = Me (4), Et (5), n-Bu (6); HBpz3 = hydrotris(1-pyrazolyl)borate; OTf = OSO2CF3, triflate] are formed on sequential reaction of (HBpz3)ReOCl2 with dialkyl zinc reagents and AgOTf. These triflate compounds are rapidly oxidized at ambient temperatures by oxygen atom donors pyridine N-oxide (pyO) and dimethyl sulfoxide (DMSO) to give (HBpz3)ReO3 (7) and the corresponding aldehyde. In the cases of 5 and 6 this transformation is quantitative. The addition of 2,6-lutidine to a low-temperature oxidation of 5 by DMSO redirects the reaction to form cis-2-butene instead of acetaldehyde. These oxidation reactions do not proceed through alkoxide intermediates, as shown by independent studies of alkoxide oxidations. Reaction of 5 with pyO or DMSO at -47°C results in the formation of intermediates which are assigned as ylide or 'trapped-carbene' complexes [(HBpz3)ReO(OH){CH(L)CH3}]OTf (L = py (8) or SMe2 (9), respectively). Mechanistic studies and analogies with related systems suggest that oxygen atom transfer to 4-6 forms [(HBpz3)ReO2R]+. Transfer of an α-hydrogen from the alkyl group to an oxo ligand then forms an alkylidene complex which is trapped by SMe2 or py to give the observed intermediates. Further oxidation of the ylide complex gives the aldehyde.
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Badin,Walters,Pease
, p. 2586 (1947)
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A dimethyl zinc preparation method
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Paragraph 0017-0019, (2020/02/10)
The invention belongs to a preparation method for dimethylzinc. The method includes the following steps that zinc halide is added into a reaction kettle under inert gas protection, then trimethylaluminum is dropwise added under the stirring condition, the reaction speed is controlled through the addition speed of the trimethylaluminum, stirring continues for reaction of 3 h-5 h after addition of the trimethylaluminum is finished, then the temperature of the reaction kettle is adjusted to be 42 DEG C-90 DEG C and kept for 2 h-3 h, and distilled Zn(CH3)2 is collected; diethylzinc is dropwise added into the reaction kettle, the temperature of the reaction kettle is controlled to be 91 DEG C-120 DEG C, distilled Zn(CH3)2 is collected, the temperature of the reaction kettle is kept within 91 DEG C-120 DEG C after addition of the diethylzinc is finished, and Zn(CH3)2 continues being collected for 1 h-3 h. According to the method, raw materials of the dimethylzinc are easy to get, reaction is simple, control is easy, industrial production is facilitated, the reaction yield is high, and the total yield reaches more than 90%.
Exchange of alkyl and tris(2-mercapto-1-t-butylimidazolyl)hydroborato ligands between zinc, cadmium and mercury
Kreider-Mueller, Ava,Quinlivan, Patrick J.,Rong, Yi,Owen, Jonathan S.,Parkin, Gerard
, p. 177 - 183 (2015/08/18)
Abstract The tris(2-mercaptoimidazolyl)hydroborato ligand, [TmBut], has been used to investigate the exchange of alkyl and sulfur donor ligands between the Group 12 metals, Zn, Cd and Hg. For example, [TmBut]2Zn reacts with Me2Zn to yield [TmBut]ZnMe, while [TmBut]CdMe is obtained readily upon reaction of [TmBut]2Cd with Me2Cd. Ligand exchange is also observed between different metal centers. For example, [TmBut]CdMe reacts with Me2Zn to afford [TmBut]ZnMe and Me2Cd. Likewise, [TmBut]HgMe reacts with Me2Zn to afford [TmBut]ZnMe and Me2Hg. However, whereas the [TmBut] ligand transfers from mercury to zinc in the methyl system, [TmBut]HgMe/Me2Zn, transfer of the [TmBut] ligand from zinc to mercury is observed upon treatment of [TmBut]2Zn with HgI2 to afford [TmBut]HgI and [TmBut]ZnI. These observations demonstrate that the phenomenological preference for the [TmBut] ligand to bind one metal rather than another is strongly influenced by the nature of the co-ligands.