Coordination ambivalence and fluxional behavior in mono- and binuclear pentacarbonyltungsten complexes of pteridine and its deaza derivatives
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Journal of Organometallic Chemistry 369 (1): 83--103 (1989)

WL(CO)5 (L = pteridine (pte), 1,5-naphthyridine, (npt), 1,4,5-triazanaphthalene (tan), 1,4,6-triazanaphthalene) and W2(CO)10L1 (L1 = pt, npt) were prepd. Unambiguous identification of coordination sites was only possible by use of high-resoln. 1H NMR because the chem. shifts and spin-spin coupling consts. are characteristically affected by W(CO)5-coordination to neighboring N centers. Fluxional behavior with respect to the peri coordination sites was obsd. for W(CO)5(1,4,5-tan) and W(CO)10(pte). Competition between the more basic pyridine or pyrimidine and the better p backdonating pyrazine N centers leads to various positions for the nondegenerate equil. between linkage isomers. Cyclic voltammetry and solvent-dependent charge transfer absorption spectra of the complexes reveal low-lying p* levels which can become populated after chem. or electrochem. redn., the spin distribution in the centrosym. binuclear complex of 1,5-naphthyridine anion radical was fully characterized using ESR and results from MO calcns. on SciFinder(R)
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