P₄S₃ and P,P′ or N,N′ Donors as Competitive Building Blocks in Copper(I) Coordination Polymers

Abstract

The synthesis and characterization of hybrid polymers combining organic P,PЈ (dppe) or N,NЈ (pyrazine) ligands and inorganic donors (P 4 S 3 ) as cross-linkers between copper(I) halide aggregates is described. As a simple model system the reaction of a mixture of P 4 S 3 , PEt 3 , and CuX (X = Cl, Br, I) was studied. According to X-ray diffraction analysis, pseudotetrahedral monomers [CuX(PEt 3 ) 2 (P 4 S 3 )] (1-3) were formed, in which P 4 S 3 coordinates through the apical phosphorus atom. Layering a mixture of P 4 S 3 , Ph 2 PCH 2 CH 2 PPh 2 (dppe), and toluene with CuCl in MeCN under diffusion conditions gives 1D-[CuCl(dppe)(MeCN)] (6), which contains (Cu 2 Cl 2 ) 2 -(μ-dppe) 2 clusters linked by another dppe ligand. The analogous reaction with CuI gives 1D-[CuI(P 4 S 3 )(dppe)] (7), which is built up of alternating trans-(Cu 2 I 2 )(P 4 S 3 ) 2 units and dppe linkers. Hybrid polymers 2D-[CuX(P 4 S 3 )(dppe)] [X = Br (8), I (9)] are formed if CH 2 Cl 2 is used instead of toluene. The 2D

Unusual Reactivity of Sodium Tetramesityltetraphosphanediide towards Cyclohexyl Isocyanide

“…[14,19] The Cu1···Cu1' distance of 2.7196 (8) (Figure 4) is shortert han the Scheme2.Proposed mechanism of the formation of 1,3,5-triphospha-1,4pentadienediide. 16(2)8)b ond angles are smaller than the values reported in the literature, [21] which also supports the possibility of am etalmetal interaction. Eur.J.…”

“…[20] The CuÀBr bonds (2.3900(5)a nd 2.4017(5) )a re shorter and the Cu-Br-Cu (69. 16(2)8)b ond angles are smaller than the values reported in the literature, [21] which also supports the possibility of am etalmetal interaction. Cuprophilic interactions have been recently demonstrated in a1 ,3-benzazaphosphole-bridged tetranuclear copper(I) acetate complexw ith the help of theoretical methods.…”

Copper

“…41 Related [P 4 S 3 ] cages have also been employed in the synthesis of copper(I) coordination polymers. 42 The linear tetraphosphine, dpmppm, was used in the stepwise construction of Au 4 Ag 2 Cu 2 rings incorporating all three coinage metals. 43 Occasionally unusual solid-state properties are associated with coordination polymers involving copper.…”