Structural and Spectroscopic Studies of Halocuprate(I) and Haloargentate(I) Complexes [M2XnX′4−n]2− |
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| Authors: | Graham A Bowmaker Prof Dr Michael I Bruce Brian W Skelton Neil Somers Allan H White |
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| Institution: | 1. Department of Chemistry, University of Auckland, Private Bag 92019, Auckland, 1142 New Zealand, Tel: (649) 373 7599 ex 88340 FAX: (649) 373 7422Department of Chemistry, University of Auckland, Private Bag 92019, Auckland, 1142 New Zealand, Tel: (649) 373 7599 ex 88340 FAX: (649) 373 7422;2. Adelaide 5005/South Australia, School of Chemistry and Physics, University of Adelaide;3. Crawley 6009/Western Australia, School of Biomedical, Biomolecular and Chemical Sciences, Chemistry M313, The University of Western Australia |
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| Abstract: | The complexes Cu2Br4]2?, Cu2I4]2?, Cu2I2Br2]2?, Cu2I3Cl]2?, Ag2Cl4]2? have been characterized as their isomorphous bis(triphenylphosphoranylidene)ammonium (Ph3PNPPh3]+ = PNP+) salts by single crystal structural determinations. All anions show the centrosymmetric doubly halogen‐bridged forms XM(μ‐X)2MX]2? with three‐coordinate metal atoms that have been observed in M2X4]2? complexes with other large organic cations. In Cu2I2Br2]2? the iodide ligands occupy the bridging positions and the bromide the terminal positions, while in Cu2I3Cl]2?, obtained in an attempt to prepare Cu2I2Cl2]2?, two of the iodide ligands occupy the bridging positions with the third iodide and the chloride ligand occupying two statistically disordered terminal positions. In Ag2Cl4]2? the distortion from ideal trigonal coordination of the metal atom is greater than in the copper complexes, but less than in other previously reported Ag2Cl4]2? complexes with organic cations. The ν(MX) bands have been assigned in the far‐IR spectra, and confirm previous observations regarding the unexpectedly simple IR spectra of Cu2X4]2? complexes. |
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| Keywords: | Copper Silver Crystal structure Binuclear complexes Vibrational spectroscopy |
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