Ethyl titanium trichloride

Erskine, Gordon J.; Vanstone, Norman B.; McCowan, James D.

doi:10.1016/s0020-1693(00)91205-2

Cited by 6 publications

(4 citation statements)

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“…Standard Schlenk and rigorous high-vacuum techniques were used throughout. EtTiCl 3 was prepared by the literature method exploiting the reaction between tetraethyllead and titanium tetrachloride . In this method a molar excess of TiCl 4 is required to remove the alkylating agent and prevent the formation of di- or triethyltitanium derivatives.…”

Section: Methodsmentioning

confidence: 99%

“…EtTiCl3 was prepared by the literature method exploiting the reaction between tetraethyllead and titanium tetrachloride. 32 In this method a molar excess of TiCl4 is required to remove the alkylating agent and prevent the formation of di-or triethyltitanium derivatives. In practice, samples of EtTiCl3 prepared via this route were invariably contaminated with substantial amounts (5-10%) of TiCl4 impurity.…”

Section: Synthesis Of Etticl3 and Etticl3(dmpe)mentioning

confidence: 99%

“…In practice, samples of EtTiCl3 prepared via this route were invariably contaminated with substantial amounts (5-10%) of TiCl4 impurity. This was removed by repeated fractional condensation in vacuo, the EtTiCl3 being retained by a trap held at 228 K. The purity of the sample was checked carefully by reference to the 1 H NMR spectrum of a CD2Cl2 solution 32 and to the IR spectrum of the vapor. 6,33 Deuterated samples of EtTiCl3 were prepared in an analogous manner, the corresponding isotopomer of Et4-Pb being synthesized by the reaction of Pb(OAc)4 with a THF solution of the appropriate version of EtMgCl (itself prepared from CHD2CD2-Cl or CH2DCH2Cl).…”

Section: Synthesis Of Etticl3 and Etticl3(dmpe)mentioning

confidence: 99%

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On the Nature and Incidence of β-Agostic Interactions in Ethyl Derivatives of Early Transition Metals: Ethyltitanium Trichloride and Related Compounds

et al. 1998

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In light of the structures and spectroscopic properties of the ethyltitanium compounds EtTiCl3 (1), and EtTiCl3(dmpe) (dmpe = Me2PCH2CH2PMe2) (2), extensive DFT calculations have been carried out to explore the structures, energetics, potential energy surfaces, and spectroscopic properties not only of these but also of related ethyl derivatives of early transition metals, M. The analysis has sought to assess the true nature of so-called β-agostic interactions in these systems and how such interactions depend on the atomic number, coordination number, valence electron (VE) count, and net charge of M. The calculations reproduce well the experimentally determined properties of 1 and 2. Analysis of wave functions indicates that, where significant β-interactions occur, the M−Cα bonding electrons are delocalized over the entire ethyl group, the marked reduction of the MCC valence angle allowing the metal atom to establish covalent bonding interactions with the β-C atom and, perhaps to a lesser extent, with its appended proximal H atom. A β-agostic alkyl group may be considered a two-electron ligand, and the main contribution to the stabilization arises from Ti···Cβ bonding. Barriers to conformational change of the M−Et unit depend inter alia on the space available in the coordination sphere of the central M atom, with rearrangement of the ethyl group to accommodate significant β-interaction being opposed by interligand repulsion. Such interaction is found not in 1, but in its dmpe adduct 2 because the increase in coordination number is offset by elongation of the Ti−C and Ti−Cl bonds and by the extra pliability of the EtTiCl3 moiety resulting from complexation by the dmpe ligand.

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Section: Methodsmentioning

confidence: 99%

Section: Synthesis Of Etticl3 and Etticl3(dmpe)mentioning

confidence: 99%

Section: Synthesis Of Etticl3 and Etticl3(dmpe)mentioning

confidence: 99%

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On the Nature and Incidence of β-Agostic Interactions in Ethyl Derivatives of Early Transition Metals: Ethyltitanium Trichloride and Related Compounds

et al. 1998

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“…Ethyltrichlorotitanium was prepared by a literature method exploiting the reaction between tetraethyllead and titanium tetrachloride. 19 In this procedure, a molar excess of was TiCl 4 required to remove the alkylating agent and prevent the formation of di-or triethyltitanium derivatives. In practice, samples of prepared via this route were invariably EtTiCl 3 contaminated with substantial amounts (5È10%) of TiCl…”

Section: Misch Data and The Concept Of Vibrational Isolationmentioning

confidence: 99%