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- Title
Exploiting the Twofold Donor Ability of Carbodiphosphoranes: Theoretical Studies of [(PPh<sub>3</sub>)<sub>2</sub>C→EH<sub>2</sub>]<sup>q</sup> (E<sup>q</sup>=Be, B<sup>+</sup>, C<sup>2+</sup>, N<sup>3+</sup>, O<sup>4+</sup>) and Synthesis of the Dication [(Ph<sub>3</sub>P)<sub>2</sub>CCH<sub>2</sub>]<sup>2+</sup>
- Authors
Celik, Mehmet Ali; Frenking, Gernot; Neumüller, Bernhard; Petz, Wolfgang
- Abstract
Quantum chemical calculations at the BP86/TZVPP//BP86/SVP level of theory have been performed for the isoelectronic series of compounds [(PPh3)2C→EH2]q (Eq=Be, B+, C2+, N3+, O4+). The equilibrium geometries and bond dissociation energies were calculated and the nature of the C→E bond was investigated with charge and energy decomposition methods. The dication [(PPh3)2C→CH2]2+ could become isolated as a salt compound with two counter ions [AlBr4]−. The X-ray structure analysis of [(PPh3)2C→CH2]2+ gave bond lengths and angles that are in good agreement with the calculated data. The geometry optimization of [(PPh3)2C→OH2]4+ gave [(PPh3)2C→OH]3+ as the equilibrium structure. Bonding analysis of [(PPh3)2C→EH2]q shows that [(PPh3)2C→BeH2] and [(PPh3)2C→BH2]+ possess donor-acceptor bonds in which the σ and π lone-pair electrons of (PPh3)2C donate into the vacant orbitals of the acceptor fragment. The multiply charged compounds are better described as substituted olefins [(PPh3)2CCH2]2+, [(PPh3)2CNH2]3+, and [(PPh3)2COH]3+, which possess electron-sharing σ and π bonds that arise from the interaction between the triplet states of [(PPh3)2C]2+ and the respective fragment CH2, (NH2)+, and (OH)+. The multiply charged cations [(PPh3)2CCH2]2+, [(PPh3)2CNH2]3+, and [(PPh3)2COH]3+ are calculated to be stable toward dissociation.
- Subjects
ISOELECTRONIC sequences; CATIONS; CHEMICAL decomposition; DENSITY functionals; DISSOCIATION (Chemistry); CHEMICAL bonds
- Publication
ChemPlusChem, 2013, Vol 78, Issue 9, p1024
- ISSN
2192-6506
- Publication type
Article
- DOI
10.1002/cplu.201300169