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Analytical and Bioanalytical Chemistry -  相似文献   

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Preparation and Spectroscopic Characterization of Bond Isomeric Halogenoselenocyanato-Osmates(IV) and -Rhenates(IV) By oxidative ligand exchange of appropriate chloro-iodo complexes of OsIV or ReIV with (SeCN)2 in CH2Cl2 or by heterogeneous reaction with Pb(SeCN)2 or AgSeCN in CH2Cl2 the new complexes cis-[OsCl4(NCSe)(SeCN)]2?, tr.-[OsCl4Br(NCSe)]2?, tr.-[OsCl4Br(SeCN)]2?, [ReCl5(NCSe)]2?, [ReCl5(SeCN)]2?, tr.-[ReCl4I(NCSe)]2?, tr.?[ReCl4(NCSe)(SeCN)]2? and tr.?[ReCl4(NCSe)2]2? are formed and isolated as pure compounds by ion exchange chromatography on DEAE-cellulose. The bond isomers are significantly distinguished by the frequencies of innerligand vibrations: n?CN(Se) > n?CN(N); n?CSe(N) > n?CSe(Se); δNCSe > δSeCN. The electronic spectra (10 K) of the solid salts reveal a bathochromic shift for the charge transfer bands of the Se isomers as compared with the corresponding N isomers. The intra-configurational transitions are observed for the OsIV complexes at 600 to 2400 and for the ReIV complexes at 500 to 1600 nm. The 77Se nmr signals of the OsIV bond isomers are registrated for Se binding in the region 970 to 1040 ppm, for N coordination downfield at 1540 to 1640 ppm.  相似文献   

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