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Cyanide‐Bridged Oligonuclear Complexes Containing Ni‐CN‐Cu and Pt‐CN‐Cu Linkages
Author(s) -
Flay MarieLouise,
Vahrenkamp Heinrich
Publication year - 2003
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.200200680
Subject(s) - chemistry , crystallography , hypsochromic shift , copper , cyanide , absorption spectroscopy , redox , stereochemistry , inorganic chemistry , physics , organic chemistry , quantum mechanics , fluorescence
The central building blocks Ni(CN) 4 2− and Pt(CN) 4 2− can be combined with one, two or four Cu II L units (L = tren, Me 6 tren, tpa) to form di‐, tri‐ and pentanuclear complexes with Ni‐CN‐Cu and Pt‐CN‐Cu linkages. Structure determinations of these and the side product [(tren)Cu−CN−Cu(tren)] (ClO 4 ) 2 reveal mostly linear M‐C‐N‐Cu arrays and cis ‐, trans ‐ and star‐like arrangements of the CN‐Cu units around the central Ni or Pt ions. The $\tilde {\nu}$ (CN) IR data for the bridging cyanides show a characteristic hypsochromic effect compared to the data for the free M(CN) 4 2− complexes. The absorption bands in the visible spectra of the oligonuclear complexes are shifted to shorter wavelengths than those of the free LCu II ‐X complexes. The Cu II /Cu I redox steps in the cyclic voltammograms allow the conclusion that there is electronic communication between the external CuL units when they are arranged in a trans ‐orientation at Pt II , but not Ni II , centers. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)