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

✍ Scribed by Andreas Biegerl; Dmitry Piryazev; Manfred Scheer; Joachim Wachter; Alexander Virovets; Manfred Zabel

• Publisher: John Wiley and Sons
• Year: 2011
• Tongue: English
• Weight: 809 KB
• Volume: 2011
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.201100444

✦ Synopsis

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)] ( ), 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)] ( ), 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