. 2021 Mar 23;11(20):11793–11803. doi: 10.1039/d0ra08764e

DFT calculated free energies^a (kcal mol⁻¹) for the transformation of the Rh–alkyne species B_X–R to the Rh–vinylidene species 10_X–R (via Pathway III) and the Rh–H species E_X–R.


X	R	TS(C-10)_X–R	C_X–R		10_X–R	TS(C-E)_X–R	E_X–R
CH₂	^tBu	+8.7	−3.0	8.9	−12.1	−2.8	−8.1
O	^tBu	+10.2	+1.3	13.9	−8.9	+0.8	−0.6
CH₂	Ar′	+7.6	−4.5	20.2	−15.7	−5.5	−11.4
O	Ar′	+9.1	−1.0	20.1	−10.9	−1.2	−4.4

DFT method = BP86-D3(BJ)-1,2-difluorobenzene/BS2//BP86/BS1. Computed energy barrier ( Inline graphic ) is relative to B_X–R. All free energies are quoted relative to 9_X (X = CH₂ and O, R = ^tBu and Ar′).

DFT calculated free energiesa (kcal mol−1) for the transformation of the Rh–alkyne species BX–R to the Rh–vinylidene species 10X–R (via Pathway III) and the Rh–H species EX–R.

DFT calculated free energies^a (kcal mol⁻¹) for the transformation of the Rh–alkyne species B_X–R to the Rh–vinylidene species 10_X–R (via Pathway III) and the Rh–H species E_X–R.