The title compound, [[Ti(C(2)H(10)N)(2)(C(11)H(10)N(3))(2)] or Ti(C(11)H(10)N(3))(2)(NEt(2))(2)], was prepared by direct reaction of 2-(N-phenyl-methyl-imino-meth-yl)-1H-imidazole and [Ti(NEt(2))(4)]. The Ti(IV) atom is in a pseudo-octa-hedral coordination environ-ment with the imidazolido-group N-atoms occupying apical positions and amido- and imino-N-atoms cis-located in the equatorial plane. The presence of two bidentate chelating ligands determines the chirality of the Ti(IV) atom. The crystallographically independent unit, except for its phenyl rings, adopts nearly pseudo-C(2) symmetry (rotation around a twofold axis passing through the Ti atom and the centre of the imino-N⋯imino-N segment). The Ti-N(amido), Ti-N(imidazolido), and Ti-N(imino) bond lengths essentially differ, increasing by approximately 0.2 Å in the series. All ligating N atoms are in a nearly planar environment, which is indicative of additional pπ-dπ donations towards the metal atom. The two diaza-metallacyclic units are planar within 0.03 and 0.05 Å.
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http://dx.doi.org/10.1107/S1600536811013183 | DOI Listing |
Inorg Chem
May 2024
Université de Strasbourg, CNRS, IC UMR 7177, F-67000 Strasbourg, France.
To deeply investigate the interaction between a tetrathiafulvalene (TTF) unit and a Ti(IV) center, a monomeric heteroleptic octahedral Ti(IV) complex containing a diimine ligand composed of a 1,10-phenanthroline core fused with a TTF fragment (ligand ) was prepared. The stable complex formulated as Ti()(), where is a 2,2'-biphenolato derivative, was efficiently synthesized by following a one-step approach. This complex and its model species [Ti()()] were fully characterized in solution, and their solid-state structures were established by single-crystal X-ray diffraction analysis.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2024
Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104, USA.
The nitrido-ate complex [(PN)Ti(N){μ-K(OEt)}] (1) (PN=(N-(2-PPr-4-methylphenyl)-2,4,6-MeCH) reductively couples CO and isocyanides in the presence of DME or cryptand (Kryptofix222), to form rare, five-coordinate Ti complexes having a linear cumulene motif, [K(L)][(PN)Ti(NCE)] (E=O, L=Kryptofix222, (2); E=NAd, L=3 DME, (3); E=NBu, L=3 DME, (4); E=NAd, L=Kryptofix222, (5)). Oxidation of 2-5 with [Fc][OTf] afforded an isostructural Ti center containing a neutral cumulene, [(PN)Ti(NCE)] (E=O, (6); E=NAd (7), NBu (8)) and characterization by CW X-band EPR spectroscopy, revealed unpaired electron to be metal centric. Moreover, 1e reduction of 6 and 7 in the presence of Kryptofix222cleanly reformed corresponding discrete Ti complexes 2 and 5, which were further characterized by solution magnetization measurements and high-frequency and -field EPR (HFEPR) spectroscopy.
View Article and Find Full Text PDFOrganometallics
October 2023
Institute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9/163-AC, A-1060 Wien, Austria.
The synthesis, characterization, and reactivity of pyrrole-based Ti(III) and Ti(IV) PNP pincer complexes are described. [P(NH)P-Pr] () reacts with [TiCl(THF)] at room temperature in the presence of NEt to afford the Ti(IV) complex [Ti(PNP)(Cl)]. This complex reacts with acetone and cyclopentanone to give complexes [Ti(PNO-Pr)(Cl)] and [Ti(PNO-Pr)(Cl)], respectively.
View Article and Find Full Text PDFJ Phys Chem A
December 2021
Department of Chemistry, Wayne State University, Detroit, Michigan 48202, United States.
The M06-2X DFT functional has been employed to examine monomeric titanium(IV) hydroperoxo catalysts that model the individual steps in the dimeric titanium(IV)-catalyzed Sharpless reaction. This is the first example of a transition structure for titanium(IV) -butyl hydroperoxide-catalyzed epoxidation that describes the molecular motion required for oxygen atom transfer. These epoxidation catalysts have been examined for both bimolecular reactions with E-2-butene and the intramolecular epoxidation of allyl alcohol.
View Article and Find Full Text PDFDalton Trans
February 2021
Gdansk University of Technology, Faculty of Chemistry, Department of Inorganic Chemistry, Gabriela Narutowicza Str. 11/12, 80-233 Gdansk, Poland.
In this work, we report a new type of reactivity of [(BDI*)Ti(Cl){η2-P(SiMe3)-PiPr2}] (1) towards ketones (BDI* = 2,6-diisopropylphenyl-β-methyldiketiminate ligand). In the reaction of 1 with acetone, cyclopentanone or cyclohexanone, a ketone moiety is inserted into Ti-Pphosphanyl or Ti-Pphosphido bonds to form complexes with a new C-P-P moiety, providing [(BDI*)Ti(Cl){η2-P(SiMe3)-PiPr2-C(Me)2O}] (2a), [(BDI*)Ti(Cl){η2-OC(Me)2P(SiMe3)-PiPr2}] (2b), [(BDI*)Ti(Cl){η2-P(SiMe3)-P(iPr)2-{C(CH2)4}O}] (3a), and [(BDI*)Ti(Cl){η2-P(SiMe3)-P(iPr)2-{C(CH2)5}O}] (4a). Starting complex 1 reacts with cyclohexanone, yielding a monocrystalline complex [{(ArN[double bond, length as m-dash]C(Me)CHC(Me)[double bond, length as m-dash]NAr)C(CH2)5O}Ti(Cl){PiPr2-P(SiMe3)C(CH2)5O}] (4d) with the insertion of two ketone molecules.
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