Sihan Li, Mirjam Schröder, Xinzhe Shi, Anke Spannenberg, Jörg Fischer, Björn Corzilius, Fabian Reiß, Torsten Beweries
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Reactions of Titanium- and Zirconium-Based 1-Metallacyclobuta-2,3-diene Complexes with Diazenes: N═N Bond Cleavage versus N–C Bond Formation and Dearomatization
The reactions of two [rac-(ebthi)Ti]- and [rac-(ebi)Zr]-based 1-metallacyclobuta-2,3-diene complexes with diazenes are described. With azobenzene, cleavage of the N═N bond is observed in the case of Zr, leading to the formation of dinuclear Zr(IV) imido complex 1. In contrast, the insertion of azobenzene into the Ti–C bond of the titanacycle produces six-membered aza-metallacycle 6, which could only be characterized by nuclear magnetic resonance spectroscopy. With geometrically restricted benzo[c]cinnoline, activation and dearomatization of the phenyl group of the substrate occur, leading to the formation of unusual mononuclear [M = Zr (3)] and dinuclear complexes [M = Ti (7)]. Reaction mechanisms leading to the formation of these unusual complexes are proposed on the basis of control experiments.
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.