Table 1 Stoichiometric and catalytic acidification experiments for the reaction of crystalline 1, 2-crypt, 3 and 4 with 2 M ethereal HCl and solutions of 1 with acids and reductants under N₂ to produce NH₃ and N₂H₄

Entry^a	Compound	Solvent	Acid	Reductant	Acid (equiv.)	Reductant (equiv.)	NH₃ (equiv.)	N₂H₄ (equiv.)	Fixed-N (equiv.)
1	1	Et₂O	2M HCl	−	>1,500	−	0.18	−	0.18
2	2-crypt	Et₂O	2M HCl	−	>1,500	−	0.43	−	0.43
3	3	Et₂O	2M HCl	−	>1,500	−	1.57	−	1.57
4	4	Et₂O	2M HCl	−	>1,500	−	2.00	−	2.00
5	−	Et₂O	[Cy₃PH][I]	KC₈	600	600	0.00	0.03	0.06
6	−	Et₂O	[Cy₃PH][I]	KC₈	600	600	0.00^b	0.03^b	0.06^b
7	1	Hexane	[Cy₃PH][I]	KC₈	10	4	0.70	0.00	0.70
8	1	Toluene	[Cy₃PH][I]	KC₈	10	4	0.07	0.00	0.07
9	1	Et₂O	[Cy₃PH][I]	KC₈	10	4	1.18	0.00	1.18
10	1	Et₂O	[Et₃NH][BPh₄]	KC₈	600	600	0.00	0.00	0.00
11	1	Et₂O	[Et₃NH][Cl]	KC₈	600	600	0.00	0.08	0.15
12	1	Et₂O	[Et₃NH][I]	KC₈	600	600	0.00	0.01	0.02
13	1	Et₂O	[Cy₃PH][BAr^F20]	KC₈	129	129	0.40	−	0.40
14	1	Et₂O	[Cy₃PH][I]	Na	600	600	0.00	0.13	0.26
15	1	Et₂O	[Cy₃PH][I]	K	600	600	0.00	0.12	0.24
16	1	Et₂O	[Cy₃PH][I]	KC₈	173	173	1.74	0.46	2.66
17	1	Et₂O	[Cy₃PH][I]	KC₈	173	173	0.34	0.12	0.58
18	1	Et₂O	[Cy₃PH][I]	KC₈	300	300	0.88	0.13	1.14
19	1	Et₂O	[Cy₃PH][I]	KC₈	600	600	0.62	0.05	0.72
20	1	Et₂O	[Cy₃PH][I]	Rb	600	600	1.11	0.07	1.25
21	1/1-¹⁵N₂	Et₂O	[Cy₃PH][I]	RbC₈	600	600	8.84/8.17^c	0.00^c	8.84/8.17^c
22	1/1-¹⁵N₂	Et₂O	[Cy₃PH][I]	RbC₈	600	600	1.49/1.12^d	0.05/0.11^d	1.59/1.34^d
23	1	Et₂O	[Cy₃PH][I]	Cs	600	600	4.94	0.06	5.06
24	1	Et₂O	[Cy₃PH][I]	CsC₈	600	600	2.61	0.03	2.67
25	4	Et₂O	[Cy₃PH][I]	RbC₈	600	600	4.43	0.00	4.43

All reactions were conducted twice to ensure reproducibility. Solutions of 1 were as follows: 1.3 mM for entries 5–7, 11, 14–16; 0.65 mM for entries 8–10, 12, 13, 17–25. Entries 1, 2, 3 and 4 were conducted with no reductant present. Entries 5 and 6 were conducted with no U-based catalyst present.
^aExperiments were performed under 1.31-bar N₂ (except for entry 17 (2.21 bar) and entry 22 (~1.0 bar)) at −78 °C, followed by warming to 25 °C and then stirring for 17 h (MC₈, M = K, Rb, Cs) or 72 h (M⁰, M = Na, K, Rb, Cs).
^bConducted under ¹⁵N₂.
^cConducted with 1-¹⁵N₂ and under ¹⁵N₂ (1.31 bar).
^dConducted with 1-¹⁵N₂ and under ¹⁵N₂ (~1.01 bar).

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