4206-67-1Relevant articles and documents
Schumann,Mueller
, p. C5 (1978)
Hydrocarbon-Soluble Bis(trimethylsilylmethyl)calcium and Calcium-Iodine Exchange Reactions at sp2-Hybrized Carbon Atoms
Koch, Alexander,Wirgenings, Marino,Krieck, Sven,G?rls, Helmar,Pohnert, Georg,Westerhausen, Matthias
, p. 3981 - 3986 (2017/10/31)
Hydrocarbon-soluble and highly reactive [(L)xCa(CH2SiMe3)2] (L = tetrahydropyran, x = 4 (2a); L = tmeda, x = 2 (2b)) is synthesized by the metathesis reaction of Me3SiCH2CaI (1-I) with KCH2SiMe3. The durability of 2a in tetrahydropyran solution at 0 °C is sufficiently high for subsequent chemical transformations. The reaction of ICH2SiMe3 with calcium in diethyl ether yields unique cage compound [(Et2O)2Ca(I)2·(Et2O)2Ca(I)(OEt)·(Et2O)Ca(I)(CH2SiMe3)] (3). We demonstrate that alkylcalcium complexes are valuable reagents for calcium-iodine exchange reactions at Csp2-I functionalities.
Elongated Gilman cuprates: The key to different reactivities of cyano- and iodocuprates
Neumeier, Maria,Gschwind, Ruth M.
, p. 5765 - 5772 (2014/05/06)
In the past the long-standing and very controversial discussion about a special reactivity of cyano- versus iodocuprates concentrated on the existence of higher-order cuprate structures. Later on numerous structural investigations proved the structural equivalence of iodo and cyano Gilman cuprates and their subsequential intermediates. For dimethylcuprates similar reactivities were also shown. However, the reports about higher reactivities of cyanocuprates survived obstinately in many synthetic working groups. In this study we present an alternative structural difference between cyano- and iodocuprates, which is in agreement with the results of both sides. The key is the potential incorporation of alkyl copper in iodo but not in cyano Gilman cuprates during the reaction. In the example of cuprates with a highly soluble substituent (R = Me 3SiCH2) we show that in the case of iodocuprates during the reaction several copper-rich complexes are formed, which consume additional iodocuprate and provide lower reactivities. To confirm this, a variety of highly soluble copper-rich complexes were synthesized, and their molecular formulas, the position of the equilibriums, their monomers and their aggregation trends were investigated by NMR spectroscopic methods revealing extended iodo Gilman cuprates. In addition, the effect of these copper-rich complexes on the yields of cross-coupling reactions with an alkyl halide was tested, resulting in reduced yields for iodocuprates. Thus, this study gives an explanation for the thus far confusing results of both similar and different reactivities of cyano- and iodocuprates. In the case of small substituents the produced alkyl copper precipitates and similar reactivities are observed. However, iodocuprates with large substituents are able to incorporate alkyl copper units. The resulting copper-rich species have less polarized alkyl groups, i.e. gradually reduced reactivities.
