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Goldstein, Michael (1963) Infrared spectroscopic studies of amine-metal halide complexes and certain organo-boron compounds. Doctoral thesis, Northern Polytechnic.
The interaction between secondary aliphatic amines, R₂NH (R = Et, Prⁿ, Prⁱ, Buⁿ, Buⁱ, Buˢ, hexylⁿ, 2-ethylhexyl, allyl, C₆H₅·CH₂; or R₂NH = pyrrolidine) and cupric bromide and/or chloride is discussed. All the bases afforded 2:1 adducts, except di-isopropylamine and di-s-butylamine with which aminolysis occurred; a 1:3 adduct was also obtained from cupric chloride and pyrrolidine.
From diethylamine and cadmium chloride, bromide, and iodide, 2:1 complexes were obtained, and these were readily converted into 1:1 adducts. Di-n-propylamine behaved similarly, but with the amines R₂NH (R = Buⁿ, Buⁱ, hexylⁿ, C₆H₅·CH₂) only 1:1 complexes could be obtained. Di-isopropylamine neither co-ordinated nor aminolysed cadmium chloride.
Zinc bromide and/or chloride afforded 1:2 adducts with diethylamine, di-n-propylamine, and di-n-butylamine; dichlorobis(diethylamine)zinc(II) showed no tendency to evolve amine other than by base exchange.
The infrared spectra of these dialkylamine complexes have been studied, and correlation of the N–H, O–N, metal–nitrogen, and metal–halogen stretching frequencies with the basic strength of the amines towards the metal halides is discussed.
The spectra in the region 400 to c. 160 cm⁻¹ of some anhydrous binary metal halides MX₂ (M = Cuᴵᴵ, Pdᴵᴵ, Ptᴵᴵ, Cdᴵᴵ, Hgᴵᴵ, Hg₂ᴵᴵ; X = Br and/or Cl) in the solid state are reported, and the results interpreted in terms of their known crystal structures.
The preparation of dihalogenobis(heterocyclic base)copper(II) complexes, CuX₂·2B (X = Cl, Br; B = pyridine, quinoline, 2-methylpyridine, 2-ethylpyridine, 2,6-dimethylpyridine) is described and their spectra (3500–20 cm⁻¹) discussed in terms of electronic, steric, and crystal packing effects.
In addition, the vibrational spectra of a series of dialkyl p-bromophenylboronates, p-Br·C₆H₄·B(OR)₂ [R = Me, Et, Prⁿ, Prⁱ, Buⁿ, Buⁱ, Buˢ, Buᵗ, Br(CH₂)₂] are compared with similar series of dialkyl phenylboronates and bis(alkylamino)phenylborons.
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