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Synthetic Oxygen Carriers Related to Biological Systems

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Synthetic Oxygen Carriers Related to Biological Systems Synthetic Oxygen Carriers Related to Biological Systems ROBERT D. JONES, DAVID A. SUMMERVILLE, and FRED BASOLO" Department of Chemistry, North western University, E vanston, lllinois 6020 1 Received September 29, 1978 Confenfs early part of 1978, no attempt has been made to totally cover all aspects of the problem. Rather we have tried to approach the I. Introduction 139 subject in such a way as to complement the other reviews al- II. Nomenclature 139 ready available.2-18Specifically we have largely restricted our 111. Nature of 02 139 attention to the synthetic approaches that have been made to IV. Nature of Bound Dioxygen 140 observe metastable metal-dioxygen complexes of biological V. Natural Oxygen Carriers 143 importance. A. Heme-Containing Proteins, Hb and Mb 143 B. Hemerythrin 146 /I. Nomenclafure C. Hemocyanin 146 VI. Synthetic 02 Carriers 147 The terminology used in this review, referring to oxygen in its A. Porphyrins 147 various forms, is similar to that used by Vaskai5 in his recent B. Schiff Bases 148 review. The term molecular oxygen as used here refers only to VII. Cobalt-Dioxygen Carriers 148 the free uncombined O2 molecule. Unless otherwise specified, A. Early Work 148 it will be used to mean the ground (32g-)state of the molecule. 6. Recent Studies on Cobalt-Dioxygen Complexes The term dioxygen has been used as a generic designation for in Nonaqueous Solutions 149 the O2 moiety in any of its several forms, and can refer to 02 in C. Cobalt-Dioxygen Complexes in either a free or combined state. The only criterion for use of this Aqueous Solution 160 term is the presence of a covalent bond between the oxygen D. Solid-state Structures 164 atoms. Thus a metal-dioxygen complex refers to a metal con- VIII. Iron-Dioxygen Carriers 166 taining the O2 group ligated to the metal center. In using this term, IX. Manganese-Dioxygen Carriers 172 no distinction is made between neutral dioxygen or dioxygen in X. Dioxygen Carriers of Other Metals 174 any of its reduced forms. A metal-superoxide or metal-peroxide XI. Addendum 174 complex is one in which the coordindated dioxygen resembles XII. Abbreviations 174 a superoxide (02-)or peroxide (OZ2-) anion, respectively. The XIII. References 175 incorporation of 02 into a metal complex to form a metal- dioxygen compound is called oxygenation (eq 1). Deoxygenation 1. lnfroducfion is the reverse of this process. Certain metal complexes provide the delicate balance re- quired to form adducts with dioxygen without the metal (M) or 111. Nature of O2 the ligands (L) being irreversibly oxidized. Such systems, known Molecular oxygen is a paramagnetic molecule, having a triplet, as oxygen carriers, are biologically utilized in the transport and 32g-ground state. The two lowest lying electronic excited states storage of molecular oxygen. The equation for adduct formation are the singlet state, 'A, and 'A,+, lying 22.53 and 37.51 (eq 1) is written as an equilibrium process. To be classified as kcal/mol above the ground state, respectively. A molecular an oxygen carrier, it is necessary that the reverse reaction, Le., orbital description of the ground state, 32,- level is the dissociation of the dioxygen complex to give M(L) and 02, be observable. In practice this process can be observed by O~KK(~SU,)~(2~0, *)2(2p~g)2( ~PT,)~(~PT, ) '( ~PT, )' lowering the partial pressure of 02,by heating the complex, or where the KK term indicates that the shells of the two oxygen by the addition of a ligand capable of replacing the bound 02. K atoms are filled. The two unpaired electrons in the 32,- ground nM(L) i-02 + [M(L)1"(02) (1) state are found in the two degenerate antibonding 2prg" orbitals (Figure I), leaving O2 with a formal bond order of two. The n=lor2 electronic configurations for O2 in its three lowest lying states The study of compounds capable of reversibly binding mo- is shown in Figure 2. lecular oxygen has received a great deal of attention for several The MO description for molecular oxygen shows a vacancy years. Several of these compounds, like the Vaskal complex, for the addition of a single electron in both of the antibonding Ir(PPh3)2(CO)(CI),involve the addition of O2to group 8 metals. 2p~,* orbitals. The addition of one or two electrons to a neutral Although the chemistry of these compounds embraces a fas- dioxygen molecule results in formation of the superoxide (Oz-) cinating and worthwhile area of investigation, this review is and peroxide (OZ2-) anions, respectively, leaving superoxide limited to a discussion of those synthetic dioxygen complexes with a bond oraer of 1.5, and the peroxide 0-0 link with a rormal that are of specific interest as models of natural oxygen carriers. bond order of one. Consistent with this assignment of bond or- Per force, this review deals largely, but not exclusively, with ders, both the 0-0 bond lengths and 0-0 bond energies fall in complexes containing the elements iron, cobalt, and manga- the order O2 > 02- > 022-.Some of the salient physical data nese. for 02,both in its neutral and ionic forms, are summarized in In writing this paper, which reviews the literature through the Table I. 0009-266517910779-0139$05.0010 @ 1979 American Chemical Society 139 140 Chemical Reviews, 1979. Vol. 79, No. 2 Jones, Summervllle, and Basolo I .o 0 2PUq v1 -c >0 2s 2s -1.0 *2sup 0 02 0 Figure 1. The molecular orbital energy-level description for 02. - 2.0 [OO]+ [om] -2 -I 0 Cool- [oo] Oxidation Number Figure 3. Frost diagram for the reduction of O2 to H202. [DO]- [@a] TABLE 1. Some Properties of the Dioxygen Moiety 0-0 bond bond distance, energy, VO-0, [oo] order compde A kcal/mol cm-I 02+ 2.5 OnAsFs 1.123’ 149.4’ 1858‘ 02 2 02 1.207* 117.2 15154.7~ [@@I + [oo ] oz(’4 2 02 1.216e 94.7‘ 1483.58 02- 1.5 KO2 1.28 1145h 022- 1 NazO2 1.49 48.8 842) L J. C. Abrahams, Q. Rev., Chem. Soc., 10,407 (1956). Reference 23. J. Shamir, J. Beneboym, and H.Classen, J. Am. Chem. Soc., 90,6223 Figure 2. The electronic configurations for the unpaired electrons in H. the 2rg orbitals of O2 in its three lowest lying states. The lower con- (1968). Reference 23. M. Kasha and A. U. Khan, Ann. N. Y. Acad. Sci., figuration represents O2 in its 38g-state, the middle ’Ag, and the upper 171, 5 (1970). ‘Calculated from the data in footnote d. 8 L. Herzberg and the 8,+ state. G. Herzberg, Astrophys. J., 105, 353 (1947). J. A. Creighton and E. R. Lippencott, J. Chem. My$.,40, 1779 (1964). S. N. Fonw and R. L. Hudson, J. Chem. Phys., 36, 2676 (1962). I J. C. Evans, J. Chem. SOC. 0,682 The primary fate of molecular oxygen in the higher biological ( 1969). organisms is its reduction to form water. This process, which occurs with the overall transfer of four electrons (eq 2), be attributed to the rather small difference in bond energies O2 + 4H+ + 46 4H20 between HOZ-and H202 to = 1.23 V, AGO = -113.5 k~al/mol~~ (2) HOP. + H+ + e F+ H202 to = 1.68 V22 (4) is highly exothermic, both under standard conditions ([Hf] = compared with the energetically favorable formation of the 0-H 1.0 M) and at biological concentrations of H+ (pH 7.4,20 t = 0.79 bond, as can be seen by a comparison of the 0-0 bond energies V, AG = -72.9 kcal/mol), making molecular oxygen a powerful (kcal/mol): oxidizing agent. O2Z3 117.2 The reduction of 02to H20proceeds, in general, via a series of one- or two-electron transfer processes. The monodynamic H02.22 55.5 nature of these processes can be seen by examining a Frost H202“ 34.3 diagramz1(Figure 3) for the 02to H20reduction in acidic media. IV. Nature of Bound Dioxygen From this diagram it can be seen that although the overall re- duction is highly exothermic, the one-electron reduction pro- In 1936, Pauling and C0ryeI1*~published their now classic cess paper on the magnetic propertiesof oxyhemoglobin. In this paper they noted that “the oxygen molecule undergoes a profound H+ e + HOz- EO = -0.32 VZ2 Oz+ + (3) change in electronic structure on combination with hemoglobin”. is quite endothermic, owing primarily to the large reduction in Since that time, the manner in which dioxygen is bound in metal 0-0 bond strength on going from O2to H02. The highly favorable complexes has proven a matter of considerable interest and reduction of the hydroperoxyl radical (H02.) to H202(eq 4) can controversy. Synthetic Oxygen Carriers In Biological Systems Chemical Reviews, 1979, Vol. 79, No. 2 141 TABLE II. Properties of Some Metal-Dloxygen Complexesa type of complex M:O structure example YO-0,cm-l 0 superoxide-like 1:l o.H Co(bzacenXpyXO2) 1128b Fe(TpivPPXI-MelmXO2) 115SC la MI Cr(TPPMpyXO2) 1 142d range 1130-1 195 Ib ,Oh / M [C02(NH3)10(02)1~+ 1122' MO [C~Z(CN)IO(~Z)~~- 1 104e range 1075-1122 peroxide-like Ila 1:l -0 Ir(COXPPhM302) 875 Ti(OEPXO2) 8980 v [Co2(CN)4(PMe2Ph)stO2)1 881 range 800-932 Ilb 2: 1 M [Co(NHdro(O2)l+ 808' M/o'o/ [CO~(CN)~O(~Z)~~- ... range 790-884 ionic dioxygen complexes K'02- 11451 2Na+, 022- 842 a The values UO-0are for the compounds listed and values for the range of VO-0were taken in part from the values given in Table Ill in ref 15.
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