Table 2.

Reaction efficiency is maximized when photocatalyst triplet state energies are within the range of 46.2–49.2 kcal/mol

entry	R	Photocatalyst	E1/2 (Pc*/Pc−) (V vs SCE)	ET (kcal/ mol)	1a (%)b	3 (%)b
1a	CF3	4b	+1.21d	60.4d	78	14
2 a	CF3	4c	+0.97e	60.1e	78	12
3 a	CF3	4a	+0.66f	49.2e	< 5	92
4 a	CF3	4d	+0.58 g	47.7g	9	85
5 a	CF3	4e	+0.61 g	46.3g	9	81
6 a	CF3	4f	+0.74g	39.2g	57	33
7 a	CF3	4g	+1.37h	46.5h	59	32
8 a	CF3	none	–	–	77	< 5
9 b	tBu	4b	+1.21d	60.4d	78	12
10 b	tBu	4c	+0.97e	60.1e	62	26
11 b	tBu	4a	+0.66f	49.2e	21	78
12 b	tBu	4d	+0.58 g	47.7g	21	73
13 b	tBu	4e	+0.61 g	46.3g	22	71
14 b	tBu	4f	+0.74g	39.2g	68	15
15 b	tBu	4g	+1.37h	46.5h	30	61
16 b	tBu	none	–	–	78	13

^aGeneral conditions: sulfamide 1a (1.0 equiv, 0.2 mmol scale), 4-bromobenzotrifluoride (1.5 equiv), photocatalyst (1 mol %), NiBr₂•glyme (5 mol %), and DBU (3.0 equiv) in MeCN (0.25 M) with stirring between two 34W blue Kessil lamps for 24 h.

^bGeneral conditions: sulfamide 1a (1.0 equiv, 0.2 mmol scale), bromo-4-(tert-butyl)benzene (1.5 equiv), photocatalyst (1 mol %), NiBr₂•glyme (10 mol %), DBU (3.0 equiv), and dtbbpy (4 mol %) in EtOH (0.25 M) with stirring between two 34W blue Kessil lamps for 24 h.

^cYields and unreacted starting material determined by ¹H NMR using an internal standard of 2,3,5,6–tetrachloronitrobenzene.

^dE_T in (kcal/mol), E_1/2 (V vs SCE) in MeCN²⁷

^eE_T in (kcal/mol), E_1/2 (V vs SCE) in MeCN ²⁸

^fE_1/2 (V vs SCE) in MeCN²⁹

^gE_T in (kcal/mol), E_1/2 (V vs SCE) in MeCN.^19c

^hE_T in (kcal/mol), E_1/2 (V vs SCE) in MeCN³⁰