Singlet–triplet energy separations in divalent five-membered cyclic conjugated C5H3X, C4H3SiX, C4H3GeX, C4H3SnX, and C4H3PbX (X = H, F, Cl, and Br)

Singlet–triplet energy gaps in cyclopenta-2,4-dienylidene, as well as its 2- or 3-halogenated derivatives, are compared and contrasted with their sila, germa, stana, and plumba analogues; at HF/6-31G* and B3LYP/ 6-311++G(3df, 2p) levels of theory. Energy gaps (ΔGt–s), between triplet (t) and singlet (s) states, appear linearly proportional to: (i) the size of the group 14 divalent element (M = C, Si, Ge, Sn and Pb), (ii) the angle ∠C–M–C, and (iii) the ΔG(LUMO–HOMO) of the singlet state involved. The magnitude of ΔGt–s, for each 2- and/or 3-substituted species studied, increases with an order of: carbenes < silylenes < germylenes < stanylenes < plumbylenes. This order reverses for the barriers of the ring puckering. The puckering occurs with more ease for every singlet, compared to its corresponding triplet form.Regardless of the group 14 element (M) employed, every 3-halo-substituted species is more stable than the corresponding 2-halo-substituted isomer. For M = Pb, Sn and/or Ge; 3-halo-substituted species have higher ΔGt–s than their corresponding 2-halo-substituted analogues. For M = Si, similar ΔGt–s are found for 2- and 3-halogenated isomers. For M = C, 3-halo-substituted species have lower ΔGt–s than their corresponding 2-halo-substituted analogues.Every cyclic singlet has a larger ∠C–M–C angle, than its corresponding cyclic triplet state, except for 3-halosilacyclopenta-2,4-dienylidenes where triplet has a larger ∠C–M–C angle than its corresponding singlet state.

Graphical abstractAb initio and DFT calculations on 2X- and/or 3X-cyclopenta-2,4-dienylidenes, and their group 14 analogues (silylenes, germylenes, stanylenes and plumbylenes; M = Si, Ge, Sn, and Pb, respectively), show linear relationships between singlet–triplet energy gaps with: (a) the size of the divalent element (M), (b) the ∠C–M–C angle, and (c) the ΔG(LUMO–HOMO) of the singlet states involved (for X = H, F, Cl, Br).Figure optionsDownload full-size imageDownload as PowerPoint slide