From Organic Azides through Titanium Triazenido Complexes to Titanium Imides. Issue 2 (16th January 2018)

• Record Type: Journal Article
• Authors: Manßen, Manfred; Weimer, Irina; Adler, Christian; Fischer, Malte; Schmidtmann, Marc; Beckhaus, Rüdiger
• Is Part Of: European journal of inorganic chemistry. Issue 2(2018)
• Page Start: 131
• Page End: 136
• Publication Date: 2018-01-16
• Subjects: Titanium -- Azides -- Fulvenes -- N ligands -- Insertion; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201701273
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : The reactions of organic azides (RN3 ; R = 2, 6‐dimesitylphenyl, SiMe3 ) with bis(η 5 :η 1 ‐pentafulvene)titanium complexes1 and titanium monopentafulvene complexes [Cp # Ti(η 5 :η 1 ‐pentafulvene)Cl] (5 ; #: R5 = H, Me) were investigated. For complexes1, insertion of the γ‐N atom of the azide into the Ti–C exo bond results in the formation of titanium triazenido complexes2 in good yields. Complexes2 undergo subsequent rearrangements in solution to titanium imido complexes3 and4 through release of N2 . Due to a haptotropic shift of the fulvene ligands, C–C coupling of the fulvenes occurs and leads to a new chelating cyclopentadienyl allyl system. By the use of the Lewis donor 4‐chlorobenzonitrile these imido complexes are stabilized. Monopentafulvene complexes5 directly generate chlorido‐bridged titanium imido complexes6 by release of N2 and the fulvene ligand. These new compounds were characterized by NMR spectroscopy and single‐crystal XRD. Abstract : Reactions of η 5 :η 1 ‐pentafulvene titanium complexes with organic azides result in the formation of titanium triazenido complexes by insertion of the γ‐N atom. These complexes rearrange after release of dinitrogen, haptotropic shift of the fulvene ligands, and C–C coupling of the fulvenes to titanium imido complexes with a new chelating cyclopentadienyl allyl system.