Slow diffusion reactions of the pentaphosphaferrocene ['CP AST'FE'('eta POT. 5-'P IND. 5')] ('CP AST'='eta POT. 5'- 'C IND. 5''ME IND. 5'. (1)) with 'CU'X (X='CL', 'BR', I) in different stoichiometric ratios and solvent mixtures result in the formation of one- and two-dimensional polymeric compounds 2-6 with molecular formula '[{'CU'('mü'-X)}-{'CP AST''FE'('mü IND.3','eta POT. 5':'eta POT. 1':'eta POT. 1'-'P IND. 5')}] IND. n' (X='CL' (2a), I (2'c)), '[{'CU'('mü'-I)}-{'CP AST''FE'('mü IND.3','eta POT. 5':'eta POT. 1':'eta POT. 1'-'P IND. 5')}] IND. n'(3), '[{'CU'('mü'-X)}-{'CP AST''FE'('mü IND.4','eta POT. 5':'eta POT. 1':'eta POT. 1'-'P IND. 5')}] IND. n' (X='CL' (4a), 'BR' (4b), I (4c), 'BR' (4'b), I (4'c)), '[{'CU IND.3''('mü'-I) IND. 2'('mü IND. 3'-I)}- {'CP AST''FE'('mü IND. 5','eta POT. 5':'eta POT. 1':'eta POT. 1':'eta POT. 1''P IND. 5')}] IND n' (5) and '[{'CU IND. 4''('mü'-X) IND. 4'(C'H IND. 3'CN)}- {'CP AST''FE'('mü IND. 7','eta POT. 5':'eta POT. 2':'eta POT. 1':'eta POT 1':'eta POT. 1'-'P IND. 5')}] IND n'(X='CL' (6a), 'BR' (6b)), respectively. The polymeric compounds have been characterised by single-crystal X-ray diffraction analyses and, for selected examples, by magic angle spinning (MAS) NMR spectroscopy. The solidstate structures demonstrate the versatile coordination modes of the cyclo-'P IND. 5' ligand of 1, extending from two to five coordinating phosphorus atoms in either 'sigma' or 'sigma'-and-'pi' fashion. In compounds 2a, 2'c and 3, two phosphorus atoms of 1 coordinate to copper atoms in a 1,2 coordination mode (2a, 2'c) and an unprecedented 1,3 coordination mode (3) to form one-dimensional polymers. Compounds 4a-c, 4'b, 4'c and 5 represent two-dimensional coordination polymers. In compounds 4, three phosphorus atoms coordinate to copper atoms in a 1,2,4 coordination mode, whereas in 5 the cyclo-'P IND. 5' ligand binds in an unprecedented 1,2,3,4 coordination mode. The crystal structures of 6a,b display a tilted tube, in which all P atoms of the cyclo-'P IND. 5' ligand are coordinated to copper atoms in 'sigma'- and 'pi'-bonding modes.Deutsche Forschungsgemeinschaft (projects Sche 384/26- 1 and Ec168/10, “Supramolecular Aggregations
