1. Cβ–Cβ Bond Fission of Metallacyclopentadiene over a Low-Valent Ditantalum Scaffold
- Author
-
Payel Laskar, Hayato Tsurugi, Hideaki Ikeda, Keishi Yamamoto, Kazushi Mashima, and Kohei Nishi
- Subjects
010405 organic chemistry ,Fission ,Chemistry ,Organic Chemistry ,Tantalum ,chemistry.chemical_element ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences ,Adduct ,Inorganic Chemistry ,Crystallography ,Moiety ,Physical and Theoretical Chemistry ,Bond cleavage - Abstract
The Cβ–Cβ bond fission of a tantallacyclopentadiene moiety bridged over low-valent Ta(V)–Ta(III) dinuclear tantalum complex 2, having an infinite structure, was facilitated by the coordination of 1,10-phenanthroline (PHEN) to give a doubly η2-alkyne-bridged ditantalum complex (phen)Cl2Ta(μ,η2-C2Et2)2TaCl2(phen) (8), while the corresponding high oxidation Ta(V)–Ta(V) complex, Cl2Ta(μ,η4-C4Et4)(μ-Cl)TaCl3 (1), afforded Cl3Ta(μ,η4-C4Et4)(μ-Cl)TaCl2(phen) (7) with an intact metallacyclopentadiene structure. Characterization of 2 was confirmed by isolating a DME adduct 9 derived from a mixture of complex 2 and DME. In contrast, no Cβ–Cβ bond cleavage was observed for azine-coordinated ditantalum complexes 5 and 6 as well as their reduced species: PHEN was found to be essentially required for the transformation of the tantallacyclopentadiene.
- Published
- 2019