Offsets between hyperconjugations, p→d donations and Pauli repulsions impact the bonding of E-O-E systems. Case study on elements of Group 14.

The nature of the E-O chemical bond (E = C, Si, Ge, Sn) is investigated in a wide range of model derivatives, such as oxonium cations, hydrogenated/methylated/fluorinated/chlorinated ethers and acyclic oligomers incorporating the E-O-E moiety. By means of density functional theory (DFT) calculations and natural bond orbital (NBO) techniques, we propose a bonding mechanism that explains the structural contrast between the organic and the inorganic counterparts of all these derivatives: the interplay between stabilizing interactions like LP(O)→σ*(E-X) hyperconjugations and LP(O)→d(E) donations with LP(O)⋯σ(E-X) vicinal Pauli repulsions (X = H, C, O, F, Cl) dictates the equilibrium structures in terms of E-O-E angles and E-O bond lengths. In addition, the present work represents the first study of oxonium ions that describes the structural discrepancies among organic derivatives and their heavier analogues. Another novel outcome for ethers and oligomers is that the two non-equivalent lone pair electrons (LPs) at the oxygen atoms impact in different manners the geometries of such derivatives, i.e. the s/p LP is correlated with the bending behaviour of the E-O-E units, while the pure p LP mainly dictates the short E-O bond distances of inorganic derivatives. Lastly, we evaluate the impact of the number of electronegative substituents, e.g. F, Cl or OEH3 groups, on the bond patterns developed for hydrogenated or methylated ethers.

Theoretical Insights into the Structural Differences between Organic and Inorganic Amines/Ethers.

The contrasting geometrical features between organic and inorganic counterparts of amines and oxanes are explained in terms of an offset between attractive (donor-acceptor) and repulsive (donor-donor) interactions. Natural bond orbital (NBO) calculations carried out at the density functional theory level of theory reveal that hyperconjugative effects in the organic amines and ethers are overcome by repulsive interactions occurring between the lone pair on the nitrogen/oxygen atom and the adjacent σ(C-R) bond orbitals. Although displaying lower energies than in the corresponding organic derivatives, the LP(X) → σ*(E-R) (X = N, O; E = Si, Ge, Sn) interactions in heavier counterparts overcome the LP(X)···σ(E-R) repulsions, impacting thus their structural behavior. In addition, NBO deletion optimizations emphasize that among hyperconjugations, back-bonding effects of the LP(X) → d(E) type dictate to a lesser extent the anomalous structures of the inorganic amines and oxanes.

Bridging a Knowledge Gap from Siloxanes to Germoxanes and Stannoxanes. A Theoretical Natural Bond Orbital Study.

Explaining the nature of the E-O chemical bond (E = Si, Ge, Sn) has been a great challenge for theoretical chemists during the last decades. Among the large number of models used for this purpose, the one based on hyperconjugative interactions sheds more light on the nature of chemical bonding in siloxanes. Starting from this concept, this study aimed to evaluate the impact of siloxane type hyperconjugative effects on the structural features of germoxanic and stannoxanic species and in addition to assess if p-d-like back-bonding interactions can also play important roles in determining the particular structures of these heavier analogues of ethers. Natural bond orbital deletion (NBO DEL) optimizations, carried out at the DFT level of theory, revealed that hyperconjugative effects dictate to a large extent the structural behavior of these species. Furthermore, this study points out that p-d back-bonding interactions also influence the equilibrium geometry of these species, although acting as a secondary electronic effect within the E-O-E moieties (E = Si, Ge, Sn).

Bis-Sulfonyl O,C,O-Chelated Metallylenes (Ge, Sn) as Adjustable Ligands for Iron and Tungsten Complexes.

The synthesis and characterization of an E2 CE2 bis-sulfonyl aryl pincer ligand and its efficiency for the stabilization of compounds containing low-valent Group 14 elements (Ge and Sn) are reported. Complexation reaction of these metallylenes with iron or tungsten complexes resulted in the modulation of the oxygen atoms of the sulfonyl groups implicated in the stabilization of the Group 14 elements, demonstrating the original adjustable character of the bis-sulfonyl O2 S-C-SO2 aryl pincer.

In silico modelling of chelate stabilized tetrylene derivatives.

The steric and electronic effects of specific ligands can play crucial roles in stabilizing unsaturated tetrylene species. In this work, hybrid density functional theory (DFT) methods, quantum theory of atoms in molecules (QTAIM) investigations and natural bond orbital (NBO) calculations are employed to evaluate the stabilization of low-valent E(ii) centers (E = Si, Ge, Sn, Pb) through the chelating effect generated by an electron-rich ligand containing the P[double bond, length as m-dash]C-P[double bond, length as m-dash]X moiety (X = O or S). Based on several types of analyses, such as the bond dissociation energy (BDE) or the interplay between attractive (i.e., charge-transfer) and repulsive (i.e., Pauli-exchange) effects, we highlight that the stabilization energy induced by chelation is up to ca. 70 kcal mol-1 for silylenes, yet slightly decreases within the heavier analogues. Moreover, it is emphasized that chelate-stabilized silylenes can form highly stable hybrid metal-metalloid complexes with transition metals (e.g., gold). Due to push-pull effects occurring in the X→Si(ii)→Au fragment, the Si(ii)→Au bonding is significantly stronger than the X→Au, P(sp2)→Au or π(C[double bond, length as m-dash]P)→Au donor-acceptor bonds, which are potentially formed by the electron-rich P[double bond, length as m-dash]C-P[double bond, length as m-dash]X unit with the AuCl fragment. These findings are supported by energy decomposition analysis (EDA) calculations.

Chalcogeno[bis(phosphaalkenyl)] germanium and tin compounds.

The first diphosphaalkenylstannylene stabilized through complexation with a carbene NHC-Sn[C(Cl)═PMes*](2)1 (Mes* = 2,4,6-tri-tert-butylphenyl; NHC = :C{N(iPr)C(Me)}(2)) was isolated and fully characterized including single crystal X-ray diffraction analysis. Its reaction with elemental sulfur rapidly gives the cyclic Sn(2)S(2) (dithiadistannetanne) derivative 3, presumably formed by dimerization of a stannathione intermediate. By contrast, its germanium analogue NHC-Ge[C(Cl)═PMes*](2)7 leads to the corresponding monomeric germathione 4 and germaselenone 5. The germaselenone was more stable than the germathione and could be structurally characterized. An unusual thermal cyclization reaction of the last one occurs with an excess of selenium to give the Ge(2)Se(3) (triselenadigermolane) ring derivative 6.

A non-symmetric sulfur-based O,C,O-chelating pincer ligand leading to chiral germylene and stannylene.

New chiral heteroleptic germanium(ii) and tin(ii) metallylenes were obtained using 1-(para-tolylsulfinyl)-3-tosyl-5-tert-butyl-benzene as a non-symmetric O,C,O-chelating pincer ligand. Crystallographic analysis and DFT calculations indicate that the non-symmetric sulfinyl-sulfonyl pincer ligand acts as an O,C,O-coordinating pincer-type-ligand with predominant sulfinyl intramolecular S[double bond, length as m-dash]O coordination to germanium(ii) and tin(ii) centers.

1,3-Digermacyclobutanes with exocyclic C=P and C=P=S double bonds.

New 1,3-digermacyclobutanes, with two exocyclic C=PMes* bonds, and the corresponding first bis(methylenethioxo)phosphoranes with C=P(S)Mes* moieties have been synthesized.

Phosphaalkenyl germylenes and their gold, tungsten and molybdenum complexes.

The new bis(phosphaalkenyl) germanium(II) compound (NHC)Ge(CCl=PMes*)(2) reacts with L(2)M(CO)(4) (M = Mo, W) to give bidentate complexes with an unexpected coordinating behaviour involving the Ge(II) centre and one phosphorus atom, and with AuI or Me(2)SAuCl to afford the monodentate complexes coordinated at the germanium(II) atom.