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P 4 S 3 and P,P′ or N,N′ Donors as Competitive Building Blocks in Copper(I) Coordination Polymers
Author(s) -
Biegerl Andreas,
Piryazev Dmitry,
Scheer Manfred,
Wachter Joachim,
Virovets Alexander,
Zabel Manfred
Publication year - 2011
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201100444
Subject(s) - chemistry , pyrazine , toluene , crystallography , halide , ligand (biochemistry) , monomer , copper , coordination polymer , polymer , dimer , stereochemistry , crystal structure , inorganic chemistry , organic chemistry , biochemistry , receptor
The synthesis and characterization of hybrid polymers combining organic P,P′ (dppe) or N,N′ (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 structures of 8 and 9 may be derived from that of 7 by connecting neighboring (CuX)(dppe) strands with pairs of inversely coordinated P 4 S 3 cages. Replacement of dppe by pyrazine (pyz) yields 3D‐[(CuCl) 4 (P 4 S 3 ) 2 (pyz)] ( 10 ) and 3D‐[(CuBr) 3 (P 4 S 3 )(pyz)] ( 12 ), respectively. The structure of 10 comprises a 3D network composed of alternating, linked 2D‐[(CuCl) 2 (P 4 S 3 )] and 2D‐[CuCl(pyz)] layers. The structure of 12 contains cradles built from opposing (CuBr) 6 rings and pairwise pyz and P 4 S 3 bridges. These cradles are organized into a 3D framework by condensation of the (CuBr) 6 rings, and the layers formed are linked by additional pyz molecules. The resulting voids are occupied by toluene molecules. The behavior of P 4 S 3 and P,P′ or N,N′ ligands as competitive building blocks is also expressed by the formation of binary P 4 S 3 /CuX or pyz/CuX polymers.