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Understanding the solubilization of Ca acetylide with a new computational model for ionic pairs

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Abstract

The unique reactivity of the acetylenic unit in DMSO gives rise to ubiquitous synthetic methods. We theoretically consider CaC2 solubility and protolysis in DMSO and formulate a strategy for CaC2 activation in solution-phase chemical transformations. For this, we use a new strategy for the modeling of ionic compounds in strongly coordinating solvents combining Born–Oppenheimer molecular dynamics with the DFTB3-D3(BJ) Hamiltonian and static DFT computations at the PBE0-D3(BJ)/pob-TZVP-gCP level. We modeled the thermodynamics of CaC2 protolysis under ambient conditions, taking into account its known heterogeneity and considering three polymorphs of CaC2. We give a theoretical basis for the existence of the elusive intermediate HC[triple bond, length as m-dash]C–Ca–OH and show that CaC2 insolubility in DMSO is of thermodynamic nature. We confirm the unique role of water and specific properties of DMSO in CaC2 activation and explain how the activation is realized. The proposed strategy for the utilization of CaC2 in sustainable organic synthesis is outlined.

Graphical abstract: Understanding the solubilization of Ca acetylide with a new computational model for ionic pairs

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Supplementary files

Article information


Submitted
29 Aug 2020
Accepted
07 Oct 2020
First published
08 Oct 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020, Advance Article
Article type
Edge Article

Understanding the solubilization of Ca acetylide with a new computational model for ionic pairs

M. V. Polynski, M. D. Sapova and V. P. Ananikov, Chem. Sci., 2020, Advance Article , DOI: 10.1039/D0SC04752J

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