Table 2.

Calculated relative enthalpies (DFT, B3LYP-D3/def2-SVP level of theory in kJ mol⁻¹) for the catalytic cycle of monometallic Ir complexes for different solvents and bases.

Intermediate.	Base	MeCN (M1)	DMSO	H2O	MeOH
[IrIII(solv)]+	DBU	0.0	0.0	0.0	0.0
	NEt3	0.0	0.0	0.0	0.0
[IrIII(base)]+	DBU	−66.7	−34.2	−86.2	−84.0
	NEt3	−9.0	22.5	−28.7	−26.2
[IrIII(η2-H2)]+	DBU	56.4	87.7	36.3	39.3
	NEt3	56.4	87.7	36.3	39.3
[IrIIIH]	DBU	−56.8	−25.8	−77.6	−73.8
	NEt3	−9.0	21.7	−30.4	−25.8
[TS3]	DBU	28.4	59.1	7.8	11.6
	NEt3	76.3	106.7	55.0	59.6
[IrIIIHCO2]	DBU	−57.4	−26.6	−78.7	−74.3
	NEt3	−9.6	21.0	−31.5	−26.3
[IrIII(solv)]+ (a)	DBU	−73.4	−73.3	−73.3	−73.4
	NEt3	−59.6	−59.7	−59.7	−59.5

^(a) With considering the formation of the [DBU(H)]HCO₂ salt.