Ruthenium(III) Catalysis in Perborate Oxidation of 5-Oxoacids

Table 3

Rate dependence on 5-oxoacid.

(a)

5-Oxoacid	10^3; (s^−1); 10^2[5-Oxoacid; (mol dm^−3); 298 K						10^3(); (s^−1); 298 K
	1.0	3.0	4.0	6.0	8.0	10.0	1.0	3.0	4.0	6.0	8.0	10.0
p-OCH3	4.92; (2.13)	10.03; (4.75)	12.31; (4.19)	16.23; (6.57)	18.91; (8.67)	21.46; (10.07)	2.78	5.28	8.11	9.66	10.24	11.39
p-CH3	2.45; (1.07)	5.01; (2.37)	6.15; (2.09)	8.11; (3.29)	9.45; (4.33)	10.73; (5.03)	1.38	2.64	4.05	4.83	5.12	5.69
p-C6H5	1.78; (0.78)	3.65; (1.73)	4.48; (1.53)	5.91; (2.39)	6.89; (3.16)	7.83; (3.67)	1.01	1.92	2.95	3.51	3.73	4.15
–H	1.61; (0.70)	3.29; (1.56)	4.04; (1.38)	5.33; (2.16)	6.21; (2.85)	7.05; (3.31)	0.91	1.73	2.66	3.17	3.36	3.74
p-Cl	0.49; (0.22)	1.01; (0.48)	1.24; (0.43)	1.64; (0.67)	1.91; (0.88)	2.17; (1.02)	0.27	0.53	0.81	0.97	1.03	1.15
p-Br	0.25; (0.11)	0.51; (0.25)	0.63; (0.22)	0.83; (0.34)	0.97; (0.45)	1.10; (0.52)	0.14	0.26	0.41	0.49	0.52	0.58
m-NO2	0.12; (0.06)	0.25; (0.12)	0.31; (0.11)	0.41; (0.17)	0.48; (0.22)	0.54; (0.26)	0.06	0.13	0.20	0.24	0.25	0.28

(b)

5-Oxoacid	10^3; (s^−1); 10^2 [5-Oxoacid; (mol dm^−3); 308 K						10^3(); (s^−1); 308 K
	2.0	3.0	4.0	6.0	8.0	10.0	2.0	3.0	4.0	6.0	8.0	10.0
p-OCH3	14.98; (4.78)	20.46; (7.66)	24.26; (8.64)	31.62; (11.95)	36.18; (16.21)	40.14; (18.86)	10.12	12.79	15.62	19.67	20.09	21.37
p-CH3	7.48; (2.39)	10.22; (3.83)	12.13; (4.32)	15.81; (5.98)	18.08; (8.11)	20.06; (9.43)	5.05	6.39	7.81	9.83	10.04	10.68
p-C6H5	5.46; (1.74)	7.46; (2.79)	8.85; (3.15)	11.54; (4.36)	13.20; (5.92)	14.64; (6.88)	3.68	4.66	5.70	7.17	7.33	7.79
–H	4.92; (1.57)	6.72; (2.52)	7.97; (2.84)	10.39; (3.93)	11.89; (5.33)	13.19; (6.20)	3.32	4.20	5.13	6.46	6.60	7.02
p-Cl	1.51; (0.49)	2.07; (0.78)	2.45; (0.88)	3.20; (1.21)	3.66; (1.65)	4.06; (1.91)	1.02	1.28	1.58	1.98	2.03	2.16
p-Br	0.77; (0.25)	1.05; (0.39)	1.25; (0.45)	1.63; (0.62)	1.86; (0.84)	2.07; (0.98)	0.51	0.65	0.80	1.01	1.03	1.10
m-NO2	0.38; (0.12)	0.52; (0.19)	0.62; (0.22)	0.81; (0.31)	0.92; (0.42)	1.02; (0.49)	0.25	0.32	0.39	0.50	0.51	0.54

(c)

5-Oxoacid	10^3; (s^−1); 10^2[5-Oxoacid; (mol dm^−3); 318 K						10^3(); (s^−1); 318 K
	1.0	2.0	3.0	4.0	6.0	8.0	1.0	2.0	3.0	4.0	6.0	8.0
p-OCH3	16.05; (5.75)	29.34; (9.25)	36.48; (12.89)	44.70; (15.51)	51.08; (22.99)	56.56; (26.89)	10.30	20.09	23.47	29.22	27.97	29.74
p-CH3	8.02; (2.87)	14.66; (4.62)	18.24; (6.45)	22.34; (7.76)	25.54; (11.49)	28.28; (13.44)	5.15	10.04	11.73	14.60	13.98	14.86
p-C6H5	5.85; (2.09)	10.70; (3.37)	13.31; (4.71)	16.31; (5.67)	18.64; (8.39)	20.14; (9.81)	3.75	7.33	8.56	10.66	10.20	10.85
–H	5.27; (1.89)	9.64; (3.04)	11.99; (4.24)	14.69; (5.10)	16.79; (7.56)	18.59; (8.84)	3.38	6.60	7.71	9.60	9.19	9.77
p-Cl	1.62; (0.58)	2.97; (0.94)	3.69; (1.31)	4.53; (1.57)	5.18; (2.33)	5.73; (2.73)	1.04	2.03	2.37	2.96	2.83	3.01
p-Br	0.82; (0.29)	1.51; (0.48)	1.88; (0.67)	2.30; (0.80)	2.64; (1.19)	2.92; (1.39)	0.52	1.03	1.21	1.50	1.44	1.53
m-NO2	0.41; (0.15)	0.75; (0.24)	0.93; (0.33)	1.14; (0.39)	1.31; (0.59)	1.45; (0.69)	0.26	0.51	0.60	0.74	0.71	0.76

^a10³[Perborate]₀ = 1.0 mol dm⁻³; 10²[H⁺] = 9.88 mol dm⁻³; *10⁴[Ru(III)] = 1.0 mol dm⁻³; HOAc—H₂O = 1 : 1% (v/v).
Parentheses values indicate the rate constant (, s⁻¹) of uncatalyzed reactions.