Abstract
The heteronuclear carbonyl complex [(NH3)2CuCo(CO)4] 1 reacts with the phosphane ligands PPh3, PEt3 and P(OMe)3. A dinuclear complex, [(PPh3),CuCo(CO)4] 2, is formed with PPh3, while trinuclear anionic [Cu{Co(CO)4}2]- species are formed with the other phosphane ligands. The crystal structure of 2 (Cu—Co = 255.2(2) pm) and the structures of two compounds with trinuclear anions, [Cu{P(OMe)3}4][Cu{Co(CO)4}2] 3 (Cu—Co = 232.64(8) and 233.10(8) pm) and PPN[Cu{Co(CO)4}2] 6 (Cu—Co = 238.1(1) and 234.3(1) pm), have been determined by X-ray crystallography. The angle Cax—Co—Ceq of tetracarbonyl cobalt compounds (i. e. the deviation from tetrahedral geometry) depends on the charge of the Co(CO)4 fragment, as calculated with the electronegativity equalization scheme of Bratsch (J. Chem. Ed. 61, 588 (1984)).

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