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. Author manuscript; available in PMC: 2019 Nov 28.
Published in final edited form as: Chem Rev. 2018 Oct 29;118(22):10840–11022. doi: 10.1021/acs.chemrev.8b00074

Table 5.

Selected Bond Lengths and Angles of Synthetic and Enzymatic Metal-“Oxy” Speciesa

entry no. complex “oxy” species 0–0 (Å) Fe-O (Å) M2–O (Å) Ml-M2 (Å) Ml–O–O M2–O–O Ml–O–O–M2
O2 NA 1.21 NA NA NA NA NA
KO2 NA 1.28 NA NA NA NA NA
H2O2 NA 1.47 NA NA NA 95° 120°
Superoxides
(1) sperm whale Mb ES1092 1.24 1.81 NA NA 122.1° NA
(2) sperm whale Mb ES1131 1.23 1.84 NA NA 115.5° NA
(3) human Hb Es69 1.24 1.87 NA NA 159.1° NA
(4) [CuII2,(UN-O)(O2)]2+c μ-1, 1-S783 1.29 NA 2.07 3.29 127.3° 103.4°
2.12 128.4° (Cu-O-Cu)
(5) [CuII2,(UN-O)(O2)]2+c μ-1, 2-S783 1.29 NA 2.02 3.49 121.4° 14.4°
2.04 123.1°
(hydro)peroxides
(6) CPO-OOH HP302 1.50 1.80 NA NA 131° NA
(7) Mb-O2d P570 1.33 1.85 NA NA 120° NA
(8) Mb-O2d P571 1.26 1.84 NA NA 119° NA
(9) [CuII(BPPA)(OOH)]+ HP701 1.46 NA 1.89 NA 114.5° NA
(10) [CuII(biot-et-dpea)(OH2)(OOH)]+ HP721 1.52 NA 1.94 NA 138.2° NA
(11) [CuII2(LEt)(OOH)]2+ HP789 1.46 NA 1.98 3.53 114.0° 125.6°
1.99 120.3° (Cu-O-Cu)
(12) [CuII2(XYL-O)(mCPBA)]2+ AcP786 1.46 NA 1.97 3.20 122.4° 108.3°
1.97 123.3° (Cu-O-Cu)
(13) [ZnII (Ts3Tren)(H2O2)]− H2P1132 1.45 NA 2.17 NA 129.8° NA
dicopper(II) trans-peroxides
(14) [{CuII(TMPA)}2 (O2)]2+ TP766 1.43 NA 1.85 4.36 107.7° 180°
(15) [{CuII(Me6Tren)}2(O2)]2+ TP758 1.37 NA 1.90 4.59 116.4° 180°
(16) [{CuII(Bz3Tren)}2(O2)]2+ TP767 1.45 NA 1.87 4.48 111.5° 180°
(17) [{CuII(Tet b)}2(O2)]2+ TP768 1.50 NA 1.92 4.57 114.9° 143.7°
1.94 115.2°
(18) [{CuII(TPANHPh)}2(O2)]2+ TP769 1.48 NA 1.90 4.69 118.5° 180°
(19) [CuII4(1L−)2(O2)(OH)2(ClO4)]+ TP1133 1.45 NA 1.96 4.18 113.7° 107.0°
(20) [CuII4(1L−)2(O2)(OH)2(ClO4)]+ TP1133 1.45 NA 1.94 4.32 113.8° 120.9°
(21) [CuII4(1L−)2(O2)(OH)2]2+ TP1134 1.37 NA 1.95 4.82 137.7° 119.8°
(22) [CuII4(1L−)2(O2)(OH)2]2+ TP1134 1.37 NA 2.02 4.85 119.6° 177.4°
(23) Cu-SSZ-13c TP805 1.35 NA 1.82 3.98 NR NR
1.83
dicopper(II) cis-peroxides
(24) [CuII2(LMe)(O2)] + CP790 1.50 NA 1.90 3.80 119.2° 65.2°
1.91 118.9°
(25) [CuII2(LEt)(O2)] + CP791 1.46 NA 1.87 3.68 101.9° 104.2°
1.88 103.6°
(26) [CuII2(UN-O)(O2)]+c CP783 1.36 NA 1.99 3.44 112.7° 71.9°
1.97 105.4°
(27) [CuII4(L−)2(O2)(OH)2(ClO4)]+ CP1133 1.45 NA 1.96 3.03 113.7° 7.0°
1.94 113.8°
(28) [CuII4(L−)2(O2)(OH)2]2+ CP1134 1.37 NA 1.95 3.90 137.7° 28.8°
2.02 119.6°
dicobalt (III) trans-peroxides (29) [{CoIII(Tren)}2(O2)(CN)]2+ TP1135 1.47 NA 1.87 4.53 113.2° 180°
(30) [{CoIII(Pytacn)}2(O2)(NCCH3)]4+c TP1136 1.40 NA 1.90 4.50 121.6° 131.9°
(31) [CoIII2(L4-)(O2)] TP1137 1.36 NA 1.93 4.15 119.4° 101.9°
1.94 117.4°
dibacolt (III) cis-peroxides
(32) [{CoIII(tmpa)}2(O2)(OH)]3+ CP1138 1.41 NA 1.84 3.26 110.8° 59.8°
1.85 112.7°
(33) [CoIII2(Oxapyme2−)(O2)(NO2)] + CP1139 1.41 NA 1.86 3.77 111.1° 96.8°
1.85 110.8°
(34) [CoIII2(LO−)(O2)(PO2Ph2)] + CP1140 1.41 NA 1.86 3.23 112.8° 57.8°
1.86 109.2°
heme-peroxo-copperb,c
(35)		 [(DCHIm)F8FeIII-O2-CuII(AN)] + TP497 1.42 1.82 1.90 4.19 121.0° 163.4°
92.4°
(36) [(DCHIm)F8FeIII-O2-CuII(AN)]+ (ArOH) TP747 1.43 1.82 1.95 4.16 124.6 130.9°
98.4
(37) [(DCHIm)F8FeIII-O2-CuII(TMPA)] + TP497 1.40 1.82 1.89 4.49 119.9° 165.2°
113.6°
(38) [(DCHIm)F8FeIII-O2-CuII(DCHIm)3] + TP919 1.37 1.83 1.96 4.16 122.7° 131.5°
100.1°
(39) [(DCHIm)F8FeIII-O2-CuII(DCHIm)4]+ TP919 1.37 1.84 1.99 4.46 121.3° 142.1°
112.2°
(40) [(DCHIm)F8FeIII-O2-CuII(DCHIm)4]+ (ArOH) TP919 1.41 1.83 2.00 4.37 123.0° 111.7°
121.0°
(41) bovine CcO (1V54) TP747 1.41 1.83 1.90 4.26 120.4° lina 128.6°
110.0°
a

Abbreviations used: ES = end-on superoxide; μ-1,1-S = superoxide bridging through one O-atom; μ-1,2-S = superoxide bridging through both O-atoms; HP = hydroperoxide; P = peroxide; AcP = acylperoxide; H2P = hydrogen peroxide bound; TP = trans-peroxide; CP = cis-peroxide

b

For entries 35–41, Ml = Fe and M2 = Cu.

C

DFT calculated structure.

d

Nonprotonated peroxide, H-bonding to the N–H of a nearby His residue.