Group 5ansa-Metallocenes: Structural and Dynamic Properties of Tetrahydroborate Complexes
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Abstract
The new compounds [Nb{(η-C5H4)X(η-C5H4)}Cl2] (X = CEt2 1a, C(C5H10) 1b, C2Me4 1c), [Nb{(η-C5H3tBu)C2Me4(η-C5H3tBu)}Cl2] 1d, [Nb{(η-C5H4)X(η-C5H4)}(η2-BH4)] (X = CEt2 2a*, C(C5H10) 2b, C2Me4 2c*, SiMe2 2e*), [Nb{(η-C5H3tBu)C2Me4(η-C5H3tBu)}(η2-BH4)] (2d*), [Nb{(η-C5H4)X(η-C5H4)}(η2-BD4)] (X = C2Me4 3c, CMe2 4), and [V{(η-C5H4)C2Me4(η-C5H4)}(η2-BH4)] (5*) have been prepared. The asterisk indicates the crystal structure has been determined. The hydrogen scrambling processes in the tetrahydroborate complexes 2a−e, 3c, 4, 5, and [Nb{(η-C5H4)CMe2(η-C5H4)}(η2-BH4)] have been studied. The free energy barrier ΔG⧧ to bridge-terminal hydrogen exchange is considerably reduced when the bridging unit imposes significant structural changes in the metallocene.
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