. 2024 Feb 6;15(11):3980–3987. doi: 10.1039/d3sc05595g

6-311+G* level)^a of the reactions of 1-CH₂ and 1-S with different nucleophiles.

System	Nucleophile	ΔG^‡	ΔE_int	ΔE_Pauli	ΔV_elstat	ΔE_orb
1-X	Nucleophile	ΔG^‡	ΔE_int	ΔE_Pauli	ΔV_elstat	ΔE_orb
1-CH₂	Me₂S CH–CN	20.7	−21.4	180.5	−109.2	−92.7
1-S	Me₂S CH–CN	19.6	−22.7	180.5	−109.7	−93.5
1-CH₂	Me₂S CH–CO₂Me	24.8	−23.0	180.9	−109.8	−94.1
1-S	Me₂S CH–CO₂Me	23.7	−24.6	181.7	−111.0	−95.2
1-CH₂	Me₂S CH–p(NO₂)C₆H₄	19.6	−19.6	138.6	−87.7	−70.4
1-S	Me₂S CH–p(NO₂)C₆H₄	18.0	−21.6	139.9	−89.2	−72.2
1-CH₂	[Cl–CH–SO₂Ph]⁻	10.3	−22.4	141.8	−87.7	−77.4
1-S	[Cl–CH–SO₂Ph]⁻	5.1	−27.6	143.5	−91.9	−49.6

Computed at the same consistent C⋯C bond-forming distance (i.e. the distance in the transition state of the 1-S process).

Computed reaction barriers (ΔG‡) and EDA terms (in kcal mol−1, computed at the ZORA-M06-2X/TZ2P//M06-2X/6-311+G* level)a of the reactions of 1-CH2 and 1-S with different nucleophiles.