- The preparation of pentafluorophenyldihaloboranes from pentafluorophenylmercurials C6F5HgR and BX3: the dramatic dependence of the reaction direction on the ligand R
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Abstract: In search of convenient preparations of C6F5BX2 (X = Cl, Br), reactions of C6F5HgR (R = C6F5, C6H5, C2H5, Br and Cl) with BX3 were studied. Under the action of BCl3 the order of the C–Hg bond cleavage is C6F5Hg–C6H5 > C6F5–HgC2H5 > C6F5–HgC6F5 >> C6F5–HgCl. With more reactive BBr3 the sequence is C6F5Hg–C6H5 > C6F5–HgC2H5 ~ C6F5Hg–C2H5 > C6F5–HgC6F5 ≥ C6F5–HgBr. During the study we found the simple way to alkyldibromoboranes which is presented by the preparation of C2H5BBr2 from C2H5HgBr and BBr3. It is the second example of synthesis of alkylmercury derivative in an addition to the earlier reported formation of cyclopropylmercurials from di(cyclopropyl)mercury and BX3. Graphic abstract: [Figure not available: see fulltext.].
- Bardin, Vadim V.,Adonin, Nicolay Yu.
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p. 1523 - 1531
(2019/07/22)
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- DIRECT TRANSFER OF ALIPHATIC AND AROMATIC SUBSTITUENTS FROM ORGANOSILATRANES TO MERCURY(II) SPECIES
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The relative reaction rates of several silatranes (derivatives of 2,8,9-trioxa-5-aza-1-silatricyclo1,5>undecane) and HgCl2 in acetone-d6 to yield the corresponding organomercury compound are of the order of e.g., 5 * 10-1 1 mol-1 sec-1 or slightly less, a rate that is unexpectedly high compared to the essentially inert parent organotrialkoxysilanes.Thus, the apical Si-C bond of the silatrane is extraordinarily susceptible to direct electrophilic attack by mercury(II).The rates decrease in the order CH2=CH, C6H5, p-ClC6H4 > CH3 > CH3CH2, CH3CH2CH2 > C6H11, ClCH2, Cl2CH, CH3CH2O.The effects of varying the solvent and the counterions are noted, and the probable mechanism is discussed.
- Nies, J. Dirk,Bellama, Jon M.,Ben-Zvi, Nava
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p. 315 - 320
(2007/10/02)
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- Cation Radicals. 48. Evidence for Electron Transfer in the Alkylation of Thianthrene Cation Radical with Diethylmercury
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Evidence is presented that reaction of thianthrene cation radical (Th(1+)) with Et2Hg in acetonitrile occurs by way of initial electron transfer.Products of reaction are thianthrene (Th), 5-ethylthianthrenium perchlorate (ThEt(1+)*ClO4(1-)), and EtHg(1+).When reaction is carried out under 18O2, not only the same products are formed but also thianthrene oxide (ThO), thianthrene dioxide (ThO2), acetaldehyde, and ethanol, all of which are enriched with 18O.Reaction therefore appears to lead initially to Et2Hg(1+) from which ethyl radicals are formed and are trapped with Th(1+) and O2.Reactions of EtO2 are believed to lead to the products containing 18O.Reaction of Ph2Hg with Th(1+) does not appear to follow this pathway.
- Sugiyama, Kazuo,Shine, Henry J.
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p. 143 - 146
(2007/10/02)
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- INFRARED, RAMAN AND FORCE FIELD STUDIES OF ETHYLMERCURY(II) HALIDES
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Vibrational assignments for Hg(C2H5)X (X=Cl, Br or I) and HgBr(C2D5) are proposed, on the basis of solution studies as far as possible.For the bromides, 21 force constants are refined in the presence of 12 constrained values from C2H5Cl and 12 of these ar
- Mink, J.,Goggin, P. L.
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p. 129 - 146
(2007/10/02)
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