- On the nature and incidence of β-agostic interactions in ethyl derivatives of early transition metals: Ethyltitanium trichloride and related compounds
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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-C 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···C(β) 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.
- Haaland, Arne,Scherer, Wolfgang,Ruud, Kenneth,McGrady, G. Sean,Downs, Anthony J.,Swang, Ole
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- ORGANOMETALLOIDAL DERIVATIVES OF THE TRANSITION METALS VII. THE THERMAL AND PHOTOCHEMICAL PROPERTIES OF TRIALKYLLEAD DERIVATIVES OF Cr, Mo AND W
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Trimethyl-and triethyllead derivatives (η5-C5H5)M(CO)3PbR3 (M = Cr, Mo, and W) have been synthesized.The trimethyllead derivatives are photochemically, and to a lesser extent, thermally unstable with respect to methyl transfer reactions that yield the corresponding (η5-C5H5)M(CO)3CH3 complex.The related triethyllead complexes behave in a distinctly different fashion exhibiting rearrangements to 5-C5H5)M(CO)3>3PbEt2 (M = W, Mo).The reactions of the Cr, Mo, and W complexes with SO2 yielded the corresponding alkyl sulphinato complexes as did the reaction of t he related Fe complex 5-C5H5)Fe(CO)2PbEt3>.
- Pannell, K. H.,Kapoor, R. N.
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