Unexpected Rearrangement Leading to Formation of a 1,3‐Bis(triphenylphosphonio)prop‐1‐en‐3‐idyl Carboxylate

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)2CCH2]2+, [(PPh3)2CNH2]3+, and [(PPh3)2COH]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)2CCH2]2+, [(PPh3)2CNH2]3+, and [(PPh3)2COH]3+ are calculated to be stable toward dissociation.

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The value of 2 J P–CO as a diagnostic parameter for the structure and thermal reactivity of carbonyl-stabilised phosphonium ylides

Aitken

Boubalouta

Chang

et al. 2017

Tetrahedron

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Unexpected Rearrangement Leading to Formation of a 1,3‐Bis(triphenylphosphonio)prop‐1‐en‐3‐idyl Carboxylate

Cited by 5 publications

References 10 publications

Phosphorus Ylides and Related Compounds

Phosphorus Ylides and Related Compounds

Exploiting the Twofold Donor Ability of Carbodiphosphoranes: Theoretical Studies of [(PPh₃)₂C→EH₂]^q (E^q=Be, B⁺, C²⁺, N³⁺, O⁴⁺) and Synthesis of the Dication [(Ph₃P)₂CCH₂]²⁺

The value of 2 J P–CO as a diagnostic parameter for the structure and thermal reactivity of carbonyl-stabilised phosphonium ylides

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Unexpected Rearrangement Leading to Formation of a 1,3‐Bis(triphenylphosphonio)prop‐1‐en‐3‐idyl Carboxylate

Cited by 5 publications

References 10 publications

Phosphorus Ylides and Related Compounds

Phosphorus Ylides and Related Compounds

Exploiting the Twofold Donor Ability of Carbodiphosphoranes: Theoretical Studies of [(PPh3)2C→EH2]q (Eq=Be, B+, C2+, N3+, O4+) and Synthesis of the Dication [(Ph3P)2CCH2]2+

The value of 2 J P–CO as a diagnostic parameter for the structure and thermal reactivity of carbonyl-stabilised phosphonium ylides

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Exploiting the Twofold Donor Ability of Carbodiphosphoranes: Theoretical Studies of [(PPh₃)₂C→EH₂]^q (E^q=Be, B⁺, C²⁺, N³⁺, O⁴⁺) and Synthesis of the Dication [(Ph₃P)₂CCH₂]²⁺