Table 1.

Comparison of Kinetic and Thermodynamic Parameters for O₂ binding and dissociation for [(L)Cu]⁺ adducts.

TMG3trenc
	kO2	k−O2	KO2
ΔH‡ or ΔH0 a	10 ± 6	45 ± 7	−40 ± 2
ΔS‡ or ΔS0 b	−70 ± 26	42 ± 34	−134 ± 11
k or K 25°C	(2.7 ± 1.2) · 107	(1.5 ± 0.8) · 107	≈ 1
k or K −80°C	(2.1 ± 1.0) · 106	(5.2 ± 2.0) · 102	(6.3 ± 1.9) · 103

PV-TMPAc
	kO2	k−O2	KO2
ΔH‡ or ΔH0 a	9 ± 1	-	-
ΔS‡ or ΔS0 b	−97 ± 7	-	-
k or K 25°C	(4.8 ± 2.8) · 107	-	-
k or K −80°C	(6.6 ± 3.5) · 105	-	-

TMPAd
	kO2	k−O2	KO2
ΔH‡ or ΔH0 a	7.62	58.0	−48.5
ΔS‡ or ΔS0 b	−45.1	105	−140
k or K 25°C	1.3 · 109	1.3 · 108	15.4
k or K −80°C	1.4–1.6 · 108	240	6.5 · 105

^aΔH, kJ mol⁻¹

^bΔS, J K⁻¹ mol⁻¹

^cIn MeTHF, this work

^dIn THF, determined through flash-and-trap method.¹³ Values for [(TMPA)-Cu] in MeTHF have been found to be the same as in THF within experimental errors.