Zusammenfassung
The reaction of the cluster salts [Cp-2*Nb(CO)(2)](n)[Co11Te7(CO)(10)] (CP* = C5Me5; n = 1, 2) with excess PMe2Ph gave the neutral, dark brown clusters [Co11Te7(CO)(6)(PMe2Ph)(4)] (5) and [Co11Te7(CO)(5)(PMe2Ph)(5)] (6) with 147 metal valence electrons. The new compounds were characterized by IR spectroscopy, elemental analyses, and mass spectrometry. The molecular structure of 6 was determined ...
Zusammenfassung
The reaction of the cluster salts [Cp-2*Nb(CO)(2)](n)[Co11Te7(CO)(10)] (CP* = C5Me5; n = 1, 2) with excess PMe2Ph gave the neutral, dark brown clusters [Co11Te7(CO)(6)(PMe2Ph)(4)] (5) and [Co11Te7(CO)(5)(PMe2Ph)(5)] (6) with 147 metal valence electrons. The new compounds were characterized by IR spectroscopy, elemental analyses, and mass spectrometry. The molecular structure of 6 was determined by X-ray crystallography. Like its precursor anion, it consists of a pentagonal-prismatic [Co11Te7] core, but with a ligand sphere composed of five CO and five PMe2Ph ligands. Detailed electrochemical studies of both reactions reveal that a stepwise substitution of CO ligands in the initial cluster anions takes place leading to intermediate [CO11Te7(CO)(10-m)(PMe2Ph)(m)](n-) ions (m = 1-5; n = 1, 2). Each of these intermediates is distinguished by at least one oxidation and two reduction waves, giving rise to a total of 21 redox couples and 27 electroactive species. The electron sponge character of the new compounds is particularly pronounced in 5, which exhibits charges n between +1 and -4 corresponding to metal valence electron counts of between 146 and 151.
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