629-35-6Relevant articles and documents
Reaction of gaseous mercury with molecular iodine, atomic iodine, and iodine oxide radicals - Kinetics, product studies, and atmospheric implications
Raofie, Farhad,Snider, Graydon,Ariya, Parisa A.
, p. 811 - 820 (2008)
Mercury is present in the Earth's atmosphere mainly in elemental form. The chemical transformation of mercury in the atmosphere may influence its bioaccumulation in the human food chain as well as its global cycling. We carried out the first kinetic and product studies of the reactions of gaseous mercury with molecular iodine, atomic iodine, and iodine oxide radicals at tropospheric pressure (～740 Torr) and 296 ± 2 K in air and in N 2 (1 Torr = 133.322 4 Pa; 0 °C = 273.15 K). Atomic iodine was formed using UV photolysis of CH2I2. IO radicals were formed by the UV photolysis of CH2I2 in the presence of ozone The reaction kinetics were studied using absolute rate techniques with gas chromatographic and mass spectroscopic detection (GC-MS). The measured rate coefficient for the reaction of Hg0 with I2 was ≤ (1.27 ± 0.58) × 10-19 cm3 molecule-1 s-1. The reaction products were analyzed in the gas phase from the suspended aerosols and from deposits on the walls of the reaction chambers using six complementary methods involving chemical ionization and electron impact mass spectrometry, GC-MS, a MALDI-TOF mass spectrometer, a cold vapor atomic fluorescence spectrometer (CVAFS), and a high-resolution transmission electron microscope (HRTEM) coupled to an energy dispersive spectrometer (EDS). The major reaction products identified were HgI2, HgO, and HgIO or HgOI. The implications of the results are discussed with regards to both the chemistry of atmospheric mercury and its potential implications in the biogeochemical cycling of mercury.
Preparation of polyfunctional diorganomercurials and their transmetallation to diorganozincs. Applications to the preparation of optically active secondary alcohols
Rozema, Michael J.,Rajagopal, Duddu,Tucker, Charles E.,Knochel, Paul
, p. 11 - 27 (2007/10/02)
Two new methods of preparation of functionalized diorganomercurials have been developed.The first method involves a substitution reaction of (ICH2)2Hg with zinc-copper reagents FG-RCu(CN)ZnI in THF/DMF at -60 deg C.Functional groups such as an ester, nitrile, ketone, phosphonate, halide, and boronic ester are tolerated in this reaction.The second method involves a reductive transmetallation between polyfunctional organozinc halides and mercurous chloride (Hg2Cl2).This very convenient procedure provides a rapid route to various functionalized diorganomercurials in good yields (61-89percent yield).The synthetic utility of these mercury organometallics is demonstrated.Their transmetallation with zinc dust (toluene, 80 deg C, 3-5 h) affords dialkylzincs which add enantioselectively to aldehydes in the presence of a catalytic amount (20 molpercent) of the norephedrine derivative 13.This transmetallation can also be used to prepare stereoselectively (E)-alkenylzinc halides (> 98percent E).Addition of Cl(H)ZrCp2 to (E)-5-chloropentenylzinc bromide in CH2Cl2 (25 deg C, 1 min) affords a 1,1-bimetallic of zinc and zirconium Cl(CH2)4CH(ZnBr)ZrCp2(Cl) which reacts stereoselectively with an aldehyde providing the (E)-disubstituted olefin (49percent yield; 100percent E).
