Tantalum complexes, reaction with pyridines

The reactivity of a remarkable electronically unsaturated tantalum methyli-dene complex, [p-MeCgH4C(NSiMe3)2]2Ta( = CH2)CH3, has been investigated. Electrophilic addition and olefination reactions of the Ta = CH2 functionality were reported. The alkylidene complex participates in group-transfer reactions not observed in sterically similar but electronically saturated analogs. Reactions with substrates containing unsaturated C-X (X = C, N, O) bonds yield [Ta] = X compounds and vinylated organic products. Scheme 117 shows the reaction with pyridine N-oxide, which leads to formation of a tantalum 0x0 complex. ... 

Reactions of Tantalum(V) and Niobium(V) Iodides with Pyridine. Both niobium(V) and tantalum(V) iodide were reduced in pyridine. In each case the di-adduct of pyridine with the metal tetraiodide was produced, along with elemental iodine as its pyridine complex. The two reduction products were identified by analysis after washing with chloroform to remove the iodine liberated in the reaction. Further identification of the tantalum product was provided by x-ray diffraction data, which compared favorably to those obtained for samples of the tetraiododi(pyridine)niobium (IV) as shown in Table V. 

Reduction of Ta(silox)3Cl2 with Na/Hg leads to a three-coordinate alkoxide complex Ta(silox)3. The coordinatively unsaturated tantalum complex is capable of cleaving H2 and O2 bonds resulting in the hydride and 0x0 complexes as illustrated in Scheme 7.14. Carbon monoxide is also split upon carbonylation of Ta(silox)3 generating the 0x0 and p-dicarbide complexes. This reaction models the C—O bond cleavage and C—C bond formation believed to occur in the Fischer-Tropsch reaction, and the ketenylidene complex Ta(silox)3(=C=C=0) was postulated as the key intermediate. On the other hand, when Ta(silox)3 was treated with pyridine and benzene, remarkable T -coordinated complexes were formed. 

Apparently the dissociation is enhanced in pyridine, owing to formation of the stable complexes of both niobium (IV) iodide and elemental iodine. Although some reduction of tantalum (V) iodide also occurred in pyridine, the analytical data suggest that this reaction was not complete, and that some unreduced tantalum (V) iodide remained in the washed product. By comparison with niobium (V) iodide, the smaller extent of reduction of tantalum (V) iodide may be accounted for in terms of the greater stability of the latter toward the dissociation shown in Equation 8. 

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