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The Reaction Of BeCl2 With Carbodiphosphorane C(PPh3)2; Experimental And Theoretical Studies

W. Petz, K. Dehnicke, Nicole Holzmann, G. Frenking, B. Neumueller
Published 2011 · Chemistry

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The use of 2-Br-fluorobenzene as the solvent permitted the isolation of the addition compound [Cl2Be(C{PPh3}2)] (5) from the reaction of the carbodiphosphorane 1 (carbon) with BeCl2 featuring a three coordinate beryllium atom. In other solvents such as THF, DCM, etc. deprotonation occurs with formation of the cations (HC{PPh3}2)+ or (H2C{PPh3}2)2+. Compound 5 was characterized by an X-ray diffraction analysis. The analysis of the bonding situation in Cl2Be1 reveals that the orbital donation comes mainly from the σ lone-pair orbital of 1, whereas the π donation is rather weak. However, the Cl2Be1 π donation appears strong enough to make the donation of a second donor species 1 unfavorable. The calculation of 1Cl2Be1 shows that the latter complex is higher in energy than 1Cl2Be and free 1. The carbodiphosphorane may bind, albeit weakly, a second BeCl2 species in the complex Cl2Be1BeCl2. The bond dissociation energies for the first and second BeCl2 fragments are De = 31.8 kcal·mol–1 and 7.0 kcal·mol–1. The dimerization of Cl2Be1 is energetically slightly endoenergetic.
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