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Reactions of 1,1′‐Diphosphaferrocene with CuCl and CuBr Resulting in Cu 4 P 4 X 4 Fe 2 ( X = Cl, Br) Complexes with Adamantane‐like Topologies
Author(s) -
Schnödt Johannes,
Winter Rainer F.,
Zabel Manfred
Publication year - 2010
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200900588
Subject(s) - tetracoordinate , acetonitrile , chemistry , crystallography , solvent , ion , ligand (biochemistry) , halide , copper , molecule , metal , atom (system on chip) , inorganic chemistry , planar , organic chemistry , biochemistry , computer graphics (images) , receptor , computer science , embedded system
Cu 4 P 4 X 4 Fe 2 ( X = Cl, Br) cages are formed upon reactions of octaethyl‐1,1′‐diphosphaferrocene (odpf) with the respective Cu I halide in CH 2 Cl 2 /CH 3 CN solvent mixtures. These cages have adamantoid Cu 4 X 4 P 2 cores with two planar anelated CuP 2 Fe rings as the flaps. Both complexes 1 and 2 feature tri‐ and tetracoordinate Cu I ions and an additional acetonitrile solvent molecule in the crystal. In 1 , the solvent molecule is coordinated to one copper ion whereas it remains uncoordinated in 2 . The tricoordinate Cu I ions show a slight pyramidalization at the metal atom and somewhat short contacts to the other tricoordinate Cu I ion in 2 or the Cu 3 ‐triangle in 1 . NMR spectroscopy revealed easy decoordination of the acetonitrile ligand from 1 and a dynamic “windshield‐wiper”‐type process that interconverts the differently coordinated phospholide rings of each odpf ligand and the tri‐ and tetracoordinate Cu I ions.