No abstract

A suspension of CuX (X ϭ Cl, Br) or AgCl in organic solvents (such as CH 2 Cl 2 ) reacts with P(C 7 H 7 ) 3 (1) in a molar ratio 1:1 to give the mononuclear adducts CuX[P(C 7 H 7 ) 3 ] (X ϭ Cl (2a), Br (2b)) and AgCl[P(C 7 H 7 ) 3 ] (3a) which crystallize as isotypic compounds in the orthorhombic space group Pnma (Z ϭ 4). In the crystal, two (of the three) cyclohepta-2,4,6-trienyl substituents are present in the boat conformation, thus establishing a loose longdistance interaction between the central double bond and the metal atom. A distorted pseudo-tetrahedral coordination sphere is assumed to exist around the metal atom, with large P-M-X angles of 165.49 (8)°(2a), 162.07(7)°(2b) and 168.54(3)°(3a), respectively. The tetrameric 1:1 adduct {Cu(µ 3 -I)[P(C 7 H 7 ) 3 ]} 4 (2c) which was obtained from CuI and 1 in boiling ethanol, has also been charac-1:1 Addukte von Kupfer(I)-und Silber(I)-Halogeniden mit dem Olefinischen Phosphan Tri(1-cyclohepta-2,4,6-trienyl)phosphan. Molkülstrukturen von CuX[P(C 7 H 7 ) 3 ] (X ‫؍‬ Cl, Br), AgCl[P(C 7 H 7 ) 3 ] und {Cu(µ 3 -I)[P(C 7 H 7 ) 3 ]} 4Inhaltsübersicht. Eine Suspension von CuX (X ϭ Cl, Br) oder AgCl in organischen Solvenzien (wie CH 2 Cl 2 ) reagiert mit P(C 7 H 7 ) 3 (1) im Molverhältnis 1:1 unter Bildung der einkernigen Addukte CuX[P(C 7 H 7 ) 3 ] (X ϭ Cl (2a), Br (2b)) und AgCl[P(C 7 H 7 ) 3 ] (3a), die als isotype Verbindungen in der orthorhombischen Raumgruppe Pnma kristallisieren (Z ϭ 4). Im Kristall liegen zwei (der drei) Cyclohepta-2,4,6-trienyl-Substituenten in der Wannenform vor und bilden so eine lockere Wechselwirkung zwischen der zentralen Doppelbindung und dem Metall-Atom aus. Es wird eine verzerrt pseudo-tetraedrische Koordinationssphäre um das Metall-Atom angenommen, in der große P-M-X Winkel von 165.49(8)°( 2a), 162.07(7)°(2b) bzw. 168.54(3)°(3a) auftreten. Das tetramere terized by X-ray crystallography (monoclinic space group P2(1)/n, Z ϭ 4); it contains all 12 cyclohepta-2,4,6-trienyl substituents in the chair conformation. The NMR spectra ( 1 H, 13 C, 31 P) of the new complexes 2a-c and 3a indicate non-rigid structures in solution. At room temperature, the 31 P NMR signal of 3a appears as a doublet with an averaged coupling constant, 1 J(Ag,P), of 700.1 Hz, whereas at Ϫ45°C the two expected doublets are clearly discernible with coupling constants 1 J( 107 Ag, 31 P) ϭ 671.0 Hz and 1 J( 109 Ag, 31 P) ϭ 774.4 Hz, respectively.

The reaction of CuCl[P(C7H7)3] (1a) with sodium hexafluoroacetylacetonate, Na(hfac), leads to (hfac)Cu[P(C7H7)3] (2a), which in the presence of excess P(C7H7)3 (a) gives (hfac)Cu[P(C7H7)3]2 (3a). Whereas the 1:2 compound 3a is a pseudo-tetrahedral copper(I) complex with relatively long Cu-P (224.85(10) and 223.75(10) pm) and Cu-O (212.7(3) and 212.0(3) pm) distances, the 1:1 complex 2a may be described as having a distorted pseudo-trigonal coordination sphere (Cu-P 214.32(11) pm, Cu-O 196.6(3) and 208.1(3) pm), although one of the cyclohepta-2,4,6-trienyl substituents develops a weak additional interaction with the metal through its central C=C double bond (Cu-C 275.1 and 272.9 pm). The molecular geometries of the tri(1-cyclohepta-2,4,6-trienyl) complexes 2a and 3a are compared with those of the known tri(cyclohexyl)phosphane complexes, (hfac)Cu[P(C6H11)3]n (n = 1 (2b) and 2 (3b)), and related compounds.

The reactions of [Cu(CH3CN)4]PF6 (1) with one or two equivalents of tri(1-cyclohepta- 2,4,6-trienyl)phosphane lead to {Cu[P(C7H7)3](CH3CN)2}PF6 (2) and {Cu[P(C7H7)3]2}PF6 (3), respectively. According to the X-ray structure analyses, the cations in both 2 and 3 contain copper(I) in a pseudo-tetrahedral coordination sphere, in which a P(C7H7)3 ligand provides one or two olefinic bonds for weak interaction with the metal.

The complex Ag(CN)[P(C7H7)3] is the first (and so far only) mononuclear 1:1 derivative of AgCN with a tertiary phosphane ligand.