COPPER(I) CARBONYL AND COPPER(II) ACETATO COMPLEXES WITH 2,2'-DIPYRIDYLAMINE AND HALIDE ANIONS - CRYSTAL AND MOLECULAR STRUCTURES OF CARBONYLCHLORO(2,2'-DIPYRIDYLAMINE)COPPER(I) AND ACETATOCHLORO(2,2'-DIPYRIDYLAMINE)COPPER(II)

摘要

Series of [Cu(I)dipyam(CO)X], [Cu(II)dipyam(CH3CO2)X] and [Cu-II(dipyam)(2)(CH3CO2)]X complexes (dipyam = 2,2'-dipyridylamine; X = Cl-, Br-, I-) were synthesized and the structures of the title compounds were determined by X-ray diffraction methods. Crystallographic details for complexes [Cu(II)dipyam(CO)CL] (1) and [Cu(II)dipyam(CH3CO2)Cl] (2) are as follows: complex 1, triclinic, space group with a = 9.944(3), b = 9.450(3), c = 7.053(3) Angstrom, alpha = 69.50(2), beta = 91.81(2), gamma = 76.33(2)degrees, Z = 2; complex 2, triclinic, space group with a = 10.093(3), b = 9.098(3), c = 7.444(2) Angstrom, alpha = 106.24(2), beta = 96.91(2), gamma = 78.87(2)degrees, Z = 2. The dry carbonyl complexes are thermostable at 100 degrees C or more, but their formation was reversible in solution even at room temperature. Thermal and chemical stabilities increase from the chloro to the iodo species. Among the acetato derivatives the chloro and bromo mono-dipyam complexes were easily formed, while the iodide gave preferentially the bis-dipyam complex. Each series of the complexes gave very similar IR spectra in the range 3800-250 cm(-1). For the carbonyl derivatives the patterns of the far-IR 250-60 cm(-1) regions were shown and the v(Cu-X) frequencies assigned. [References: 30]