Einkernige und zweikernige Kupfer(I)‐Komplexe vom Typ LCuCl, LCu2Cl2und LCu2ClX [L = P(C6H4CH2NMe2‐2)3; X = Br, I]

The title compounds 3‐5are accessible by treatment of P(C6H4CH2NMe2‐2)3(1) with CuX (2a: X = Cl, 2b: X = Br, 2c: X = I) in the ratio of 1:1 or 1:2 in very good yields. Reaction of 1with equimolar amounts of 2aaffords the copper(I) chloride [P(C6H4CH2NMe2‐2)3]CuCl (3). With a further equivalent of 2ahomobimetallic [P(C6H4CH2NMe2‐2)3]Cu2Cl2(4) is formed, which also can be synthesized by the reaction of 1with two equivalents of 2a. Complex 3reacts with CuX (X = Br, I)to afford [P(C6H4CH2NMe2‐2)3]Cu2ClX (5a: X = Br; 5b: X = I) in which mixed halides are present. The newly synthesized complexes 3‐5were characterized by elemental analyses, by their IR‐, 1H‐, 13C{1H}‐ and 31P{1H}‐NMR spectra as well as by mass spectrometrical studies. The solid‐state structures of complexes 3and 4are reported. Mononuclear 3crystallizes in the monoclinic space group P21/c with the cell parameters a = 14.285(2), b = 10.853(2), c = 17.425(2) Å , β = 103.310(10)?, V = 2628.9(7) Å 3and Z = 4 with 4053 observed unique reflections; R1= 0.0314. The crystal structure of 3consists of monomeric molecules with planar coordinated copper(I) centres (CuClNP). Homobimetallic 4crystallizes in the monoclinic space group P21/n with a = 23.905(4), b = 10.874(3), c = 25.314(5), β = 99.130(10)?, V = 6497(2) /Aring; 3and Z = 4 with 9021 observed unique reflections; R1= 0.0480. In 4one of two copper(I) centres possesses a distorted trigonal‐pyramidal environment, while the other one is almost square‐pyramidal coordinated. The Cu2Cl2segment resembles to a building block which is set up by a contact ion pair consisting of Cu+and [CuCl2]‐, respectively.