Binuclear dinitrogen complexe of aryl- and benzyldicyclopentadienyltitanium(III) compounds |
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Authors: | JH Teuben |
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Institution: | Laboratorium voor Anorganische Chemie, Rijksuniversiteit, Zernikelaan, Groningen The Netherlands |
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Abstract: | The preparation of the deep-blue diamagnetic dinitrogen complexes (Cp2TiR)2N2 with R=C6H5, o-, m-, p-CH3C6H4, C6F5, CH2C6H5 is described. Their chemical and physcial properties confirm the formulation in which the R groups are σ-bonded to the Cp2Ti moiety, and the two nitrogen atoms are equivalent. The heats of formation of the complexes from Cp2TiR and N2 in toluene have been determined from spectrophotometric data; for R=C6H5, o-, m-, p-CH3C6H4, C6F5, CH2C6H5, the values are ?18, ?9, ?17, ?20, ?17 and ?14 kcal·mol?1, respectively. The solid complexes vary markedly in thermal stability, and are extremely air sensitive. The complexed nitrogen can be completely reduced with sodium naphthalene; after hydrolysis of the products, NH3 and N2H4 are obtained. In the thermolysis of the solids, some of the nitrogen is reduced. |
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