Coordination Polymers Based on [Cp*FeACHTUNGTRENUNG(h5-P5)]:\ud MAS NMR Studies

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

Spin crossover in phosphorus- and arsenic-bridged cyclopentadienyl- manganese(ii) dimers

Manganocene reacts with LiE(SiMe3)2 (E = P or As) to give [(η5-Cp)Mn{μ-E(SiMe3)2}]2, where E = P (1) or As (2). The temperature dependence of the magnetic susceptibility in 1 and 2 is due to antiferromagnetic exchange and to spin-crossover (SCO). Compound 2 shows two-step SCO with hysteresis, involving high-spin (S = 5/2) and intermediate-spin S = (3/2) Mn(II)

CCDC 863319: Experimental Crystal Structure Determination

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures

CCDC 912664: Experimental Crystal Structure Determination

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures

CCDC 863320: Experimental Crystal Structure Determination

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures

CCDC 863318: Experimental Crystal Structure Determination

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures

CCDC 816707: Experimental Crystal Structure Determination

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures

CCDC 863317: Experimental Crystal Structure Determination

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures