TY - JOUR

T1 - Understanding Solubilization of Ca Acetylide with a New Computational Model for Ionic Pairs

AU - Полынский, Михаил Вячеславович

AU - Сапова, Мария Дмитриевна

AU - Анаников, Валентин Павлович

PY - 2020

Y1 - 2020

N2 - Constructing the carbon framework from a carbon-neutral source: a new computational model for ionic pairs in solution based on DFTB MD and DFT helps to propose a strategy for sustainable organic transformations with solid CaC 2 . The unique reactivity of the acetylenic unit in DMSO gives rise to ubiquitous synthetic methods. We theoretically consider CaC 2 solubility and protolysis in DMSO and formulate a strategy for CaC 2 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 CaC 2 protolysis under ambient conditions, taking into account its known heterogeneity and considering three polymorphs of CaC 2 . We give a theoretical basis for the existence of the elusive intermediate HCC–Ca–OH and show that CaC 2 insolubility in DMSO is of thermodynamic nature. We confirm the unique role of water and specific properties of DMSO in CaC 2 activation and explain how the activation is realized. The proposed strategy for the utilization of CaC 2 in sustainable organic synthesis is outlined.

AB - Constructing the carbon framework from a carbon-neutral source: a new computational model for ionic pairs in solution based on DFTB MD and DFT helps to propose a strategy for sustainable organic transformations with solid CaC 2 . The unique reactivity of the acetylenic unit in DMSO gives rise to ubiquitous synthetic methods. We theoretically consider CaC 2 solubility and protolysis in DMSO and formulate a strategy for CaC 2 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 CaC 2 protolysis under ambient conditions, taking into account its known heterogeneity and considering three polymorphs of CaC 2 . We give a theoretical basis for the existence of the elusive intermediate HCC–Ca–OH and show that CaC 2 insolubility in DMSO is of thermodynamic nature. We confirm the unique role of water and specific properties of DMSO in CaC 2 activation and explain how the activation is realized. The proposed strategy for the utilization of CaC 2 in sustainable organic synthesis is outlined.

UR - https://www.mendeley.com/catalogue/a65a4881-0b62-3235-ad2f-cf47874a32f0/

U2 - 10.1039/D0SC04752J

DO - 10.1039/D0SC04752J

M3 - Article

VL - 11

SP - 13102

EP - 13112

JO - Chemical Science

JF - Chemical Science

SN - 2041-6520

IS - 48

ER -