Table 2.

Correlation of Selectivity Factor Q₀ with Catalytic Reaction Outcomes

entry	thiol	amide X=	*Ir(lll)	kPCET amide(M−1s−1)	KA amide(M−1)	kPCET thiol(M−1s−1)	KA thiol(M−1)	Q0	% yieldb	% recoveryb
1	PhSH	H	Ir-1	8.4×109	1050	9.5×109	200	96 : 4	100	0
2	PhSH	COMe	Ir-1	3.0×109	1500	9.5×109	200	91 : 9	100	0
3	PhSH	CN	Ir-1	9.3×108	3550	9.5×109	200	87 : 13	100	0
4	PhSH	H	Ir-2	1.1×109	1050	3.6×109	200	86 : 12	100	0
5	PhSH	COMe	Ir-2	1.8×108	1500	3.6×109	200	62 : 38	80	9
6	PhSH	CN	Ir-2	6.8×107	3550	3.6×109	200	57 : 43	8	85
7	3,5-(CF3)2C6H3SH	H	Ir-1	8.4×109	1050	8.3×109	2100	78 : 22	95	0
8	3,5-(CF3)2C6H3SH	H	Ir-2	1.1×109	1050	2.2×109	2100	64 : 36	85	0
9	3,5-(CF3)2C6H3SH	COMe	Ir-1	3.0×109	1500	8.3×109	2100	56 : 44	60	30
10	3,5-(CF3)2C6H3SH	CN	Ir-1	9.3×108	3550	8.3×109	2100	47 : 53	13	62
11	3,5-(CF3)2C6H3SH	COMe	Ir-2	1.8×108	1500	2.2×109	2100	23 : 77	10	47
12	3,5-(CF3)zC6H3SH	CN	Ir-2	6.8×107	3550	2.2×109	2100	18 : 82	0	84
13	C6F5SH	H	Ir-1	8.4×109	1050	4.0×109	5600	75 : 25	91	0
14	C6F5SH	H	Ir-2	1.1×109	1050	1.0×109	5600	61 : 39	61	23
15	C6F5SH	COMe	Ir-1	3.0×109	1500	4.0×109	5600	56 : 44	17	70
16	C6F6SH	CN	Ir-1	9.3×108	3550	4.0×109	5600	44 : 56	3	54
17	C6F5SH	COMe	Ir-2	1.8×108	1500	1.0×109	5600	24 : 76	trace	54
18	C6F5SH	CN	Ir-2	6.8×107	3550	1.0×109	5600	18 : 82	0	88
			In the following two entries, [thiol] = 0.04 M, [base] = 0.005 M
19	PhSH	H	Ir-2	1.1×109	1050	3.6×109	200	81 : 19	100	0
20	C6F6SH	H	Ir-2	1.1×109	1050	1.0×109	5600	35 : 65	15	50

^aReactions performed on 0.05 mmol scale.

^bYield and recovery assessed after 12h by ¹H-NMR relative to an internal standard.