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Synthesis of Low-Valent Dinuclear Group?14 Compounds with Element-Element Bonds by Transylidation.

ABSTRACT: Dinuclear low-valent compounds of the heavy main group elements are rare species owing to their intrinsic reactivity. However, they represent desirable target molecules due to their unusual bonding situations as well as applications in bond activations and materials synthesis. The isolation of such compounds usually requires the use of substituents that provide sufficient stability and synthetic access. Herein, we report on the use of strongly donating ylide-substituents to access low-valent dinuclear group?14 compounds. The ylides not only impart steric and electronic stabilization, but also allow facile synthesis via transfer of an ylide from tetrylene precursors of type ^R Y₂ E to ECl₂ (E=Ge, Sn; ^R Y=TolSO₂ (PR₃ )C with R=Ph, Cy). This method allowed the isolation of dinuclear complexes amongst a germanium analogue of a vinyl cation, [(^Ph Y)₂ GeGe(^Ph Y)]⁺ with an electronic structure best described as a germylene-stabilized Ge^II cation and a ylide(chloro)digermene [^Cy Y(Cl)GeGe(Cl)^Cy Y] with an unusually unsymmetrical structure.

SUBMITTER: Mohapatra C

PROVIDER: S-EPMC7756224 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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Synthesis of Low-Valent Dinuclear Group 14 Compounds with Element-Element Bonds by Transylidation.

Mohapatra Chandrajeet C Darmandeh Heidar H Steinert Henning H Mallick Bert B Feichtner Kai-Stephan KS Gessner Viktoria H VH

Chemistry (Weinheim an der Bergstrasse, Germany) 20201019 66

Dinuclear low-valent compounds of the heavy main group elements are rare species owing to their intrinsic reactivity. However, they represent desirable target molecules due to their unusual bonding situations as well as applications in bond activations and materials synthesis. The isolation of such compounds usually requires the use of substituents that provide sufficient stability and synthetic access. Herein, we report on the use of strongly donating ylide-substituents to access low-valent din ...[more]

PMID: 32954596

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Project description:The structures and bonding in the heavier group 14 element olefin analogues [E{CH(SiMe3)2}2]2 and [E{N(SiMe3)2}2]2 (E = Ge, Sn, or Pb) and their dissociation into :E{CH(SiMe3)2}2 and :E{N(SiMe3)2}2 monomers were studied computationally using hybrid density functional theory (DFT) at the B3PW91 with basis set superposition error and zero point energy corrections. The structures were reoptimized with the dispersion-corrected B3PW91-D3 method to yield dispersion force effects. The calculations generally reproduced the experimental structural data for the tetraalkyls with a few angular exceptions. For the alkyls, without the dispersion corrections, dissociation energies of -2.3 (Ge), +2.1 (Sn), and -0.6 (Pb) kcal mol-1 were calculated, indicating that the dimeric E-E bonded structure is favored only for tin. However, when dispersion force effects are included, much higher dissociation energies of 28.7 (Ge), 26.3 (Sn), and 15.2 (Pb) kcal mol-1 were calculated, indicating that all three E-E bonded dimers are favored. Calculated thermodynamic data at 25 °C and 1 atm for the dissociation of the alkyls yield ?G values of 9.4 (Ge), 7.1 (Sn), and -1.7 (Pb) kcal mol-1, indicating that the dimers of Ge and Sn, but not Pb, are favored. These results are in harmony with experimental data. The dissociation energies for the putative isoelectronic tetraamido-substituted dimers [E{N(SiMe3)2}2]2 without dispersion correction are -7.0 (Ge), -7.4 (Sn), and -4.8 (Pb) kcal mol-1, showing that the monomers are favored in all cases. Inclusion of the dispersion correction yields the values 3.6 (Ge), 11.7 (Sn), and 11.8 (Pb) kcal mol-1, showing that dimerization is favored but less strongly so than in the alkyls. The calculated thermodynamic data for the amido germanium, tin, and lead dissociation yield ?G values of -12.2, -3.7, and -3.6 kcal mol-1 at 25 °C and 1 atm, consistent with the observation of monomeric structures. Overall, these data indicate that, in these sterically-encumbered molecules, dispersion force attraction between the ligands is of greater importance than group 14 element-element bonding, and is mainly responsible for the dimerization of the metallanediyls species to give the dimetallenes. In addition, calculations on the non-dissociating distannene [Sn{SiMe t Bu2}2]2 show that the attractive dispersion forces are key to its stability.

Dataset Information

Synthesis of Low-Valent Dinuclear Group?14 Compounds with Element-Element Bonds by Transylidation.

Publications

Synthesis of Low-Valent Dinuclear Group 14 Compounds with Element-Element Bonds by Transylidation.

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