RT info:eu-repo/semantics/article
T1 The Puzzling Monopentamethylcyclopentadienyltitanium(III) Dichloride Reagent: Structure and Properties
A1 García Castro, María
A1 García Iriepa, Cristina
A1 Horno Martín, Estefanía del
A1 Martín Alonso, Avelino
A1 Mena Montoro, Miguel
A1 Pérez Redondo, Adrián
A1 Temprado Morena, Manuel
A1 Yélamos Sánchez, Carlos
K1 Química
K1 Chemistry
AB Following the track of the useful titanocene [Ti(η5-C5H5)2Cl] reagent in organic synthesis, the related half-sandwich titanium(III) derivatives [Ti(η5-C5R5)Cl2] are receiving increasing attention in radical chemistry of many catalyzed transformations. However, the structure of the active titanium(III) species remains unknown in the literature. Herein, we describe the synthesis, crystal structure, and electronic structure of titanium(III) aggregates of composition [{Ti(η5-C5Me5)Cl2}n]. The thermolysis of [Ti(η5-C5Me5)Cl2Me] (1) in benzene or hexane at 180 ºC results in the clean formation of [{Ti(η5-C5Me5)Cl(μ-Cl)}2] (2), methane and ethene. The treatment of 1 with excess pinacolborane in hexane at 65 ºC leads to a mixture of 2 and the paramagnetic trimer [{Ti(η5-C5Me5)(μ-Cl)2}3] (3). The X-ray crystal structures of compounds 2 and 3 show Ti‒Ti distances of 3.267(1) and 3.219(12) Å, respectively. Computational studies (CASPT2//CASSCF and BS DFT methods) for dimer 2 reveal a singlet ground state and a relatively large singlet-triplet energy gap. Nuclear magnetic resonance (NMR) spectroscopy of 2 in aromatic hydrocarbon solutions and DFT calculations for several [{Ti(η5-C5Me5)Cl2}n] aggregates are consistent with the existence of an equilibrium between the diamagnetic dimer [{Ti(η5-C5Me5)Cl(μ-Cl)}2] and a paramagnetic tetramer [{Ti(η5-C5Me5)(μ-Cl)2}4] in solution. In contrast, complex 2 readily dissolves in tetrahydrofuran to give a green-blue solution from which blue crystals of the mononuclear adduct [Ti(η5-C5Me5)Cl2(thf)] (4) were grown.
SN 0020-1669
YR 2019
FD 2019-04-15
LK http://hdl.handle.net/10017/38390
UL http://hdl.handle.net/10017/38390
LA eng
NO Ministerio de Economía y Competitividad de España, Universidad de Alcalá
DS MINDS@UW
RD 07-jun-2023