Novel Copper(I) Clusters with 2‐(Diphenylphosphanyl)anilide Ligands. Synthesis and Crystal Structures of [Cu₆X₂(NHR)₄] (X = Cl, Br, I; R = C₆H₄‐2‐PPh₂)

Abstract

Treatment of copper(I) halides CuX (X = Cl, Br, I) with lithium 2-(diphenylphosphanyl)anilide [Li(HL)] in THF led to the formation of hexanuclear copper(I) complexes [Cu 6 X 2 (HL) 4 ] [X = Cl (1), Br (2), I (3)]. In compounds 1-3, the copper atoms are in a distorted octahedral arrangement and the amide ligands adopt a μ 3 -κP,κ 2 N bridging mode. Additionally there are two μ 2 -bridging halide ligands. 203 Each of the [Cu 6 X 2 (HL) 4 ] clusters comprises two copper atoms, which are surrounded by two amide nitrogen atoms in an almost linear coordination [Cu-N: 186.2(3)-188.0(3) pm] and four copper atoms, which are connected to an amide N atom, a P atom, and a halogen atom in a distorted trigonal planar fashion [Cu-N: 199.6(3)-202.3(3) pm)].

Multinuclear Cu(I) Clusters Featuring a New Triply Bridging Coordination Mode of Phosphaamidinate Ligands

“…26 Octahedral or distorted octahedral assemblies are common for hexanuclear Cu(I) clusters as evidenced by clusters H , 27 I , 28 and J . 29 In contrast, the arrangement of Cu(I) atoms in 3 defines an antiprism rather than an octahedron.…”

“…Many hexacopper clusters based on either Cu­(I) or Cu­(II) are reported in the literature, featuring quite different assemblies of Cu atoms (Figure ). − The hexacopper cluster type E consists of four 5-coordinate Cu­(II) atoms located at four alternative vertices of a central defective cubane unit with two μ 3 - and two μ 2 -O atoms, and two satellite Cu­(II) atoms connect to the cubane via μ 2 -O atoms . The cluster type F consists of two 6-coordinate Cu­(II) trimer units bridged by two nitrate ions, while G possesses a coplanar assembly of 5-coordinate Cu­(II) atoms .…”

“…The cluster type F consists of two 6-coordinate Cu­(II) trimer units bridged by two nitrate ions, while G possesses a coplanar assembly of 5-coordinate Cu­(II) atoms . Octahedral or distorted octahedral assemblies are common for hexanuclear Cu­(I) clusters as evidenced by clusters H , I , and J . In contrast, the arrangement of Cu­(I) atoms in 3 defines an antiprism rather than an octahedron.…”