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Ti(IV) and Ti(III) complexes using the PCP ligand have been synthesized (PCP = CH-2,6-(CHPBu)). The [PCP]Li synthon can be reacted with TiCl(THF) to form (PCP)TiCl () in limited yields due to significant reduction of the titanium synthon. The Ti(III) complex (PCP)TiCl () has been further characterized. This can have half an equivalent of halide abstracted to form [{(PCP)TiCl}{μ-Cl}][B(CF)] () and can also be methylated, forming (PCP)TiMe (). All the Ti(III) complexes have been characterized using EPR and X-ray crystallography, giving insight into their electronic structures, which are further supported by DFT calculations.
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http://dx.doi.org/10.1021/acs.organomet.2c00662 | DOI Listing |
Chem Sci
August 2025
Department of Chemistry, University of Pennsylvania 231 South 34th Street Philadelphia PA 19104 USA
Using an Earth-abundant transition metal to mediate formation and splitting of C-C σ-bonds, in response to electrical stimuli, constitutes a promising strategy to construct complex organic skeletons. Here, we showcase how [ BuN][N] reacts with an isocyanide adduct of a tetrahedral and high-spin Ti complex, [(Tp )TiCl] (1), to enact N-atom transfer, C-N bond formation, and C-C coupling, to form a dinuclear complex, [(Tp )Ti{AdN(N)C-C(N)NAd}Ti(Tp )] (3), with two Ti ions bridged by a disubstituted oxalimidamide ligand ( Bu = -butyl, Tp = hydrotris(3--butyl-5-methylpyrazol-1-yl)borate, Ad = 1-adamantyl). Magnetic and computational studies reveal two magnetically isolated d Ti ions, and electrochemical studies unravel a reversible two-electron oxidation at -0.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, PA, 19104, USA.
Carbon dioxide capture and functionalization sequesters carbon dioxide in more robust products and offers a viable route to reducing greenhouse gas emissions. We present herein a unique molecular Ti oxo anion that reversibly binds CO to allow both its sequestration and functionalization. The reduction of [(PN)Ti═O] (1) [PN = (2-PPr-4-methylphenyl)(mesityl)amide] with KC and 2.
View Article and Find Full Text PDFInorg Chem
July 2025
Département de Chimie, Université de Sherbrooke, 2500 Blvd de l'Université, Sherbrooke, QC J1K 2R1, Canada.
Heteroanionic materials such as oxynitrides offer a unique platform for tailoring electronic and structural properties. In this work, titanium dioxide (TiO) was heated under ammonia (NH) gas to create titanium oxynitride (TiON) compounds. A combination of the indophenol blue method and thermogravimetric analysis (TGA) was used to quantitatively determine the composition of the bulk powder.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
July 2025
Kekulé-Institut für Organische Chemie und Biochemie, Universität Bonn, Gerhard-Domagk-Straße 1, 53121, Bonn, Germany.
We describe the identification of an active Ti(salen) catalyst for the radical arylation of epoxides by a cyclic voltammetry study of mechanism-based predictors, such as the redox potentials of the complexes and their EC-equilibria, for the success of catalysis. Surprisingly, by far the most active catalyst features an uncommon tetrasubstituted ligand backbone, which renders chloride binding to the active Ti(III) species less favorable, thereby increasing catalyst activity due to improved substrate binding. Catalysis is most efficient in the "green" solvent ethyl acetate and can be initiated using base metals as well as electrochemical methods for the reduction of the Ti(salen)-precatalyst.
View Article and Find Full Text PDFJ Am Chem Soc
May 2025
Department of Chemistry Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama-cho, Toyonaka, Osaka 560-8531, Japan.
Regioselective hydroaminoalkylation of alkenes via α-C-H bond activation of alkylamines is an efficient process for the preparation of complex alkylamines minimizing stoichiometric waste. Herein, we report that a combination of Cp*TiMe and AlMe catalyzes the branch-selective hydroaminoalkylation of 1-alkenes, including styrene derivatives and 1,3-dienes, with -methylaniline derivatives. Kinetic studies reveal that the active species are generated from generated Cp*TiMe(NMePh) and alkylaluminum.
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