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The three-center-four-electron tetrel bond
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry. (Erdelyi group)ORCID iD: 0000-0003-3798-3322
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2018 (English)Conference paper, Oral presentation with published abstract (Refereed)
Abstract [en]

We present a thermodynamically stable complex that possesses a three-center-four-electron (3c4e) tetrel bond [1,2], formed by capturing a reactive carbenium ion with a bidentate Lewis base. We report NMR spectroscopic, titration calorimetric and reaction kinetic evidences for the structure of this pentacoordinate species and discuss the properties of its tetrel bond, [N˜˜˜∙∙∙C∙∙∙˜˜˜N]+, in comparison with the analogous halogen, [N˜˜˜∙∙∙X∙∙∙˜˜˜N]+ and hydrogen, [N∙∙∙˜˜˜H∙∙∙˜˜˜N]+, bonds [3]. The necessity of the involvement of a bidentate Lewis base for the formation of a stable 3c4e tetrel bond is demonstrated by providing spectroscopic and crystallographic evidence, that a monodentate Lewis base induces a reaction rather than stabilizing the reactive species. A vastly decreased Lewis basicity of the bidentate ligand or reduced Lewis acidity of the carbenium ion weakens — or even prohibits — the formation of the pentacoordinate species, whereas synthetic modifications facilitating attractive orbital overlaps promote it. As the geometry of the pentacoordinate complex resembles the SN2 transition state, it may provide a model system for the investigation of fundamental reaction mechanisms and chemical bonding theories [4].

References

1. G.C. Pimentel J. Chem. Phys. 1951, 19, 446-448

2. R.H. Crabtree Chem. Soc. Rev. 2017, 46, 1720-1729.

3. S.B. Hakkert, M. Erdelyi J. Phys. Org. Chem. 2015, 95, 2572-2578

4. Karim, N. Schultz, H. Andersson, B. Nekoueishahraki et al, 2018, submitted.

Place, publisher, year, edition, pages
2018.
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-371866OAI: oai:DiVA.org:uu-371866DiVA, id: diva2:1274769
Conference
Interactions Involving Group 14 - 16 Elements as Electrophilic Sites: A World Parallel to Halogen Bond, 9th – 10th June 2018; Greenville, SC; USA
Available from: 2019-01-03 Created: 2019-01-03 Last updated: 2019-09-26Bibliographically approved

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Andersson, HannaErdélyi, Máté

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