. 2019 Jun 4;220:58–70. doi: 10.1039/c9fd00038k

Rate constants obtained by NMR spectroscopy.

Catalyst: [Au(IPr)X]^a		k _NMR = k₁ + k₂	k ₁ (dm³ mol⁻¹ min⁻¹)	k ₂ (dm³ mol⁻¹ min⁻¹)	k ₁₁ (dm³ mol⁻¹ min⁻¹)	k ₂₂ (dm³ mol⁻¹ min⁻¹)
X	BU	k _NMR = k₁ + k₂	k ₁ (dm³ mol⁻¹ min⁻¹)	k ₂ (dm³ mol⁻¹ min⁻¹)	k ₁₁ (dm³ mol⁻¹ min⁻¹)	k ₂₂ (dm³ mol⁻¹ min⁻¹)
OTf^a	—	11.8 ± 1.5	3.2 ± 1.0	8.7 ± 0.6	1.6 ± 0.8	65 ± 49
OTf^a	iPr-BU*H₂SO₄	26.5 ± 1.6	7.5 ± 1.7	18.9 ± 3.5	4.7 ± 3.1	846 ± 759
ClO₄^a	—	11.2 ± 2.2	3.1 ± 1.0	8.0 ± 1.1	1.5 ± 0.6	92 ± 77
ClO₄^a	iPr-BU*H₂SO₄^a	24.5 ± 3.4	6.2 ± 1.9	18.2 ± 1.4	3.1 ± 0.8	189 ± 99
PF₆^a	—	10.9 ± 1.5	2.8 ± 0.7	8.0 ± 0.7	1.2 ± 0.4	100 ± 85
PF₆^a	iPr-BU*H₂SO₄^a	22.1 ± 0.6	5.7 ± 1.0	16.5 ± 1.5	3.6 ± 1.0	571 ± 515
BF₄^a	—	7.6 ± 1.4	2.2 ± 0.6	4.1 ± 0.6	0.1 ± 0.1	1.8 ± 0.1
BF₄^a	iPr-BU*H₂SO₄^a	24.8 ± 2.9	7.3 ± 1.4	17.2 ± 1.2	3.0 ± 0.9	59 ± 2
SbF₆^a	—	12.0 ± 2.8	3.1 ± 1.0	8.8 ± 1.8	1.1 ± 0.1	100 ± 81
SbF₆^a	iPr-BU*H₂SO₄^a	28.8 ± 0.7	7.2 ± 0.6	21.6 ± 0.9	2.7 ± 0.2	105 ± 38
OTf^b	—	5.1 ± 0.1	1.5 ± 0.2	3.6 ± 0.3	0.6 ± 0.6	485 ± 240
OTf^b	Bn-BU^b	4.6 ± 0.8	1.3 ± 0.1	3.3 ± 0.8	0.6 ± 0.6	405 ± 231
ClO₄^b	—	6.4 ± 1.6	1.6 ± 0.1	4.7 ± 1.4	0.9 ± 0.9	578 ± 531
ClO₄	Bn-BU^b	5.2 ± 1.3	1.3 ± 0.1	3.9 ± 1.1	0.7 ± 0.7	403 ± 307
PF₆^b	—	5.0 ± 0.6	1.6 ± 0.4	3.5 ± 0.2	1.9 ± 0.1	1654 ± 1335
PF₆	Bn-BU^b	4.0 ± 0.5	1.2 ± 0.1	2.8 ± 0.5	0.6 ± 0.6	796 ± 630
BF₄^b	—	1.8 ± 0.8	1.0 ± 0.3	0.8 ± 0.5	0.1 ± 0.1	791 ± 761
BF₄	Bn-BU^b	1.7 ± 0.2	0.9 ± 0.2	0.9 ± 0.1	0.1 ± 0.1	197 ± 132
SbF₆^b	—	4.6 ± 0.1	1.4 ± 0.2	3.2 ± 0.1	1.5 ± 0.1	779 ± 452
SbF₆	Bn-BU^b	3.6 ± 0.2	1.2 ± 0.1	2.5 ± 0.2	0.6 ± 0.6	759 ± 567
Cl	Bn-BU^b^,^c		No reaction

CD₃OD : CD₂Cl₂ (1 : 0.08): 1.25 mol% [Au(IPr)X] with or without 1.25 mol% iPr-BU*H₂SO₄.

In CD₃OD : CD₂Cl₂ (1 : 2.4): 1.25 mol% [Au(IPr)X] with or without 1.25 mol% Bn-BU.

The solution of Au(IPr)Cl and Bn-BU was mixed for 24 hours.