Abstract
Interaction of Li(CH2SiMe3) with Cul gives [{Cu(CH2SiMe3)}4] a thermally stable, light-petroleum-soluble, colourless copper(I) alkyl, which by cryoscopy is a tetramer in benzene and a hexamer in cyclohexane. An X-ray crystal-structure determination at –40 °C shows that the complex consists of discrete centrosymmetric units containing a square plane of copper atoms with the methylene carbons lying in the same plane and bridging the edges. Crystals are monoclinic with a= 6.355(4), b= 12.636(7), c= 17.938(11)A, β= 90.84(5)°, space group P21/c. Relevant distances and angles are: Cu–Cu 2.417 and Cu–C (mean) 2.02 A; Cu–Cu–Cu 89.8, 90.2, Cu–C–Cu (mean) 73.5, and C–Cu–C (mean) 163.5°. Decomposition (thermal or photochemical) occurs via a homolytic path. Reactions with some organic halides (C3H5Br, Phl, SiMe3Cl, or PhCH2Br) are outlined, showing for the most part simple metathetical X–CH2SiMe3 exchanae, but less readily than with alkyls of Li or Mg. Addition of Li(CH2SiMe3) appears to yield Li[Cu(CH2SiMe3)2].
Published Version
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