Chemistry of the thermally generated, molybdenum-centered radicals {η5-C5H5Mo(CO)2L} (L = CO, PPh3)
作者:Philip R. Drake、Michael C. Baird
DOI:10.1016/0022-328x(89)88046-5
日期:1989.3
compounds [η5-C5H5Mo(CO)2L]2 (L = CO, PPh3) exist in solution solely as the metalmetal bonded dimers. no chemical evidence being found for the presence of small equilibrium amounts of the corresponding monomers η5-C5H5Mo(CO)2L}. However, the latter are readily synthesized via hydrogenatomabstraction by the trityl radicalfrom the hydrides η5-C5H5Mo(CO)2LH. The thus-formed radicals are very reactive and
与此相反,以他们的铬类似物,化合物[η 5 -C 5 H ^ 5的Mo(CO)2 L] 2(L = CO,PPH 3)存在于溶液中单独用作metalmetal连接的二聚体。无化学证据被发现的小型平衡量的相应单体η的存在5 -C 5 H ^ 5的Mo(CO)2 L}。然而,后者可容易地通过氢原子夺取由三苯甲基从氢化物η自由基合成5 -C 5 H ^ 5的Mo(CO)2LH。如此形成的自由基具有很高的反应性,并且除了二聚作用外,它们还参与了各种原子提取和配体取代反应。对这些反应的产物分布的分析为十七电子中间体的中间体提供了明确的证据。
[EN] TRIPHENYLCARBENIUM SALTS OF GROUP 13 FLUOROARYL COMPLEXES<br/>[FR] SELS TRIPHENYLCARBENIUM DE COMPLEXES FLUOROARYLES DU GROUPE 13
申请人:DOW GLOBAL TECHNOLOGIES INC
公开号:WO2004048388A1
公开(公告)日:2004-06-10
Triphenylcarbenium salts of halo(poly)gallate or halo(poly)aluminate complexes, a process for making the salts and the use of the foregoing compounds as cocatalysts for the polymerization of addition polymerizable monomers is disclosed.
This invention provides a compound comprising fluorinated aminoborate monoanion of the formula:
[R1R2R3N—BaHbFc]−1 I
methods for preparing the same, and uses thereof, where R1, R2, R3, a, b, and c are those defined herein.
Carbon−Fluorine Bond Hydrogenolysis in Perfluoroethyl−Iridium Complexes To Give HFC-134a Involves Heterolytic Activation of H<sub>2</sub>
作者:Russell P. Hughes、Stefan Willemsen、Alex Williamson、Donghui Zhang
DOI:10.1021/om020225d
日期:2002.7.1
Cp*Ir(PMe3)(CFDCF3)(O2CCH3). These results are consistent with external protonation of the CF bond and migration of the originally present H (or D) from Ir to C and suggest that the previously reported CF bond hydrogenolysis using dihydrogen proceeds via heterolytic activation of the H2 molecule at iridium.
oxidative conditions. However, little is known about the speciation of Cp*Co species during catalysis. We now show that key intermediates, Cp*CoIII metallacycles derived from 2-phenylpyridine (phpy-H), react swiftly in solution with one-electron oxidants to irreversibly collapse by a cyclocondensation of the organic ligands to afford cationic alkaloids in yields of >70%. A low-temperature EPRanalysis of