Calculations for Boron catalytic cycle

DOI: https://doi.org/10.14469/hpc/4462 Access code qh3z-nz2a

See https://www.ch.ic.ac.uk/rzepa/talks/durham18m/d17.html For scheme, see https://www.ch.ic.ac.uk/rzepa/talks/durham18m/d9.html (Figure 9 in article) and 10.14469/hpc/4462 What is 4450

B-O-B cycle using Me-B with original GD3 dispersion

Free Energy for location in ELN	DOI at repository	Description/comment
-1083.013169	10.14469/hpc/4493	reactant with amine
-1082.990382	10.14469/hpc/4523	TS2, Proton transfer via acid (amine on N) = 14.3
-1082.974577	10.14469/hpc/4548	TS2, Proton transfer via acid, with amine on acid
-1082.972113	10.14469/hpc/4373	TS4 (acetic acid carrier, open) (25.8)
-1082.978943	10.14469/hpc/4503	TS4 (acetic acid carrier, closed) (21.5)
-1082.980915	10.14469/hpc/4515	TS4 (acetic acid carrier, open) (20.3)
-1082.998307	10.14469/hpc/4492	pre-TS4 PT to amine as carrier 9.3
-1082.976160	10.14469/hpc/4490	TS4, amine carrier, closed), 23.2
-1082.979733	10.14469/hpc/4512	TS4, amine carrier, open) 21.0
-1083.017643	10.14469/hpc/4464	Product (=-28.5)/reactant for regeneration, -2.8 from initial reactant
Regeneration
-1083.017643	10.14469/hpc/4464	Product 1st =reactant=resting for regeneration = 0.0 (-1083.011253 = 4.0 for bound amide)
-1082.997352	10.14469/hpc/4451	TS5 = -15.8 (amine on acid)
-1083.004664	10.14469/hpc/4453	TS5 (amine on amide, DG = 8.1 wrt reactant, or 23.0 vs ionic resting state?
-1083.015728	10.14469/hpc/4481	TI4 = +1.2
-1083.027406	10.14469/hpc/4463	pre-TI4 ionic semi-open form
-1083.028459	10.14469/hpc/4461	pre-TI4 ionic semi-open form, -5.7 lower than reactant
-1083.041324	10.14469/hpc/4452	TI4 ionic O=C-O-B closed form cul-de-sac, -14.9 lower than reactant
-1083.007681	10.14469/hpc/4522	TS6 water loss 6.3
-1083.014387	10.14469/hpc/4522	TI5, water gone -0.8
-1083.013174	10.14469/hpc/4467 10.14469/hpc/4501	TS7 Final closure +2.8 (wrt resting for regeneration) (+17.7 wrt ionic resting state)
-1083.020284	10.14469/hpc/4468	Final product of regeneration (catalyst + MeCO2H+MeNH2=amide-H2O), + H2O) -1.7

B-O-B cycle using Ph-B with GD3 dispersion

-1466.540018	10.14469/hpc/4567	reactant with amine
-1466.508739	10.14469/hpc/7401	TS4, (acetic acid carrier, closed), 19.6
-1466.513759	10.14469/hpc/4568	TS4 (acetic acid carrier, open) 16.5
-1466.508556	10.14469/hpc/4571	TS4, amine carrier, closed) 19.7
-1466.510658	10.14469/hpc/7402	TS4, amine carrier, open) 18.4
-1466.550040	10.14469/hpc/7403	TI4, reactant=resting for regeneration (non-ionic)
-1466.576720	10.14469/hpc/4519	TI4 (ionic) -16.7
-1466.531400	10.14469/hpc/7404	TS5 regeneration 11.7 (28.4)
-1466.547544	10.14469/hpc/4635	Final product of regeneration (catalyst + MeCO2H+MeNH2=amide-H2O), + H2O)

B-O-B cycle using CF3CH2O-B with GD3BJ dispersion

-1908.013973	10.14469/hpc/7405	reactant with amine, 0.0
-1908.013592	10.14469/hpc/7406	TI1, +0.23
-1907.986281	10.14469/hpc/7407	TS4, (acetic acid carrier, closed), 17.4
-1907.987620	10.14469/hpc/7408	TS4 (acetic acid carrier, open) 16.5
-1907.988246	10.14469/hpc/4619	TS4, amine carrier, open 16.1
-1907.983258	10.14469/hpc/7409	TS4, amine carrier, closed 19.3
-1908.025908	10.14469/hpc/7410	TI4, reactant=resting for regeneration (non-ionic) -7.5
-1908.048836	10.14469/hpc/7411	TI4 (ionic) -21.9
-1907.993894	10.14469/hpc/7412	TS5 regeneration 20.0 (34.4)
-1908.021750	10.14469/hpc/4640	Final product of regeneration (catalyst + MeCO2H+MeNH2=amide-H2O), + H2O) -4.9

B-N-B Cycle using Me-B with GD3 dispersion, Figure 13.

-1102.385276	10.14469/hpc/4559	TI1, isomer 1
-1102.386998	10.14469/hpc/4553	isomer 2 = 0.0
-1102.384306	10.14469/hpc/4556	isomer 3
-1102.364028	10.14469/hpc/4557	TS1, PT 14.4 using acid as transfer agent
-1102.355209	10.14469/hpc/4552	TS2 = 19.9
-1102.398759	10.14469/hpc/4561	Product = -7.4, = 0.0 for regeneration
-1102.410792	10.14469/hpc/4560	Ionic intermediate = -14.9
-1102.376151	10.14469/hpc/4562	TS5 + 5.7
-1102.387948	10.14469/hpc/4566	Final product of regeneration -0.6

Pervasive Delocalisation Error Causes Spurious Proton Transfer in Organic Acid-Base Co-Crystals LC-wHPBE PBE1PBE, see https://doi.org/10.1002/anie.201809381