Lukyanov M. Copper(I) pi-complexes with N-allyl derivatives of aminonitriles: synthesis and stereochemistry

By means of the alternating-current electrochemical technique 20 new copper(I) compounds with some aminonitriles and N-allyl derivatives of aminonitriles have been obtained and X-ray structurally investigated. Among them are 16 copper(I) pi-compounds: 7 complexes with 3-(allylamino)propanenitrile (apn): [Cu(apn)Cl], [(H+apn)Cu2Cl3], [(H+apn)Cu2Br3], [(H+apn)CuNO3]NO3, [(H+apn)Cu(H2O)BF4]BF4•H2O, [(H+apn)Cu(NH2SO3)2], [(H+apn)Cu(H2O)2]SiF6; 8 – with 3-(diallylamino)propanenitrile (dapn): [(H+dapn)CuCl2], [(H+dapn)CuCl1,94Br0,06], [(H+dapn)CuBr2], [Cu(dapn)ClO4], [(H+dapn)CuClO4]ClO4•H2O, [Cu(dapn)BF4], [(H+dapn)CuBF4]BF4•H2O, [(H+dapn)Cu(H2O)]SiF6•H2O; 1 with 3-[(2-hydroxyethyl)(allyl)amino]propanenitrile (аhepn) – [(H+ahepn)CuCl2]; 3 complexes with: 3,3'-piperazine-1,4-diyldipropanenitrile (pipdpn) - [{(H+)2pipdpn}0,5CuCl2], 3-[(2-hydroxyethyl)amino]propanenitrile (hepn) - [(H+hepn)CuCl2], 3,3'-iminodipropanenitrile (idpn) - [(H+idpn)Cu3Cl4], and one compound witn electrostatic bond with 3,3'-(ethane-1,2-diyldiimino)dipropanenitrile (endpn) - [(H+)2endpn]0,5CuCl2.Copper(I) halide pi-complexes with N-allyl derivatives of aminonitriles differ essentially from those with ionic copper(I) salts by the coordination behaviour of the ligands as to Cu(I) centres: in the structure of copper(I) halide complexes only C=C bond of the allylic group is coordinated to the metal atom; contrary to this, in the compounds with ionic copper(I) salts (CuNO3, CuSO3NH2, CuClO4, CuBF4, Cu2SiF6) C=C-bond as well as N-atom from the cyano-group are coordinationally active to Cu(I) atoms. The (E)H...X bonds (E = N, O, C; X = Cl, Br, OClO3, ONO2, FBF3, OSO2NH2, F6Si) play a significant role in a crystal structure formation of the complexes discussed.