Lewis-Base Adducts of Group 11 Metal(I) Compounds. XXXVII. A Novel Isomerism in the Heterobimetallic 1:1 Adducts of Copper(I) Halides With Tris(dithiocarbamato)cobalt(III)

Abstract

Reaction of copper(I) iodide with tris (N,N- dipropyl -and N, N- diisopropyl-dithiocarbamato )cobalt(III), [Co(S₂CNR₂)₃ ≡ Co( dtc )₃](R = Pr or Prⁱ ), yields 1:1 adducts which have been characterized by single-crystal X-ray structure determination. Crystals of the propyl species are monoclinic, P2₁/c, a 13.722(7), b 16.854(7), c 16.787(8)Ǻ, β 121.66(3)°, R was 0.056 for N_o 2834 'observed' reflections. The isopropyl derivative is orthorhombic, Ccca , a 33.93 (1), b 13.616(8), c 14.574(5)Ǻ; R was 0.075 for N_o 726. Each adduct is dimeric [Co( dtc )₃](CuI₂Cu)[Co( dtc )₃]; the propyl derivative has crystallographically imposed i symmetry, whereas the isopropyl adduct has quasi-222 symmetry. Thus, the chiralities of the pair of Co( dtc )₃ moieties in the dipropyl adduct are opposite, whereas in the isopropyl adduct they are the same.