Superoxo- compounds

This chapter is largely concerned with the structural chemistry of Fe, Co, Ni, Pd, and Pt, for the most part in finite complexes. The structures of the simpler compounds of these and other transition metals have been described under Halides, Oxides, etc. in the appropriate chapters. Other groups of compounds described in earlier chapters include hydrido compounds, oxo-, peroxo-, and superoxo-compounds, carbonyls, and nitrosyls, in Chapters 11, 12, and 18, respectively. We note here a few general points. 

The ligand changes effect large variations in their dioxygen reactivity The reaction of [Cu(TMPA)(MeCN)] with O2 in propionitrile at low temperatures initially generates an unstable copper(II)-superoxo compound (A.max 410 nm, 4,000 M cm 747 nm s 1,000 M cm ) and then... 

A dramatic ligand effect was observed for the oxygenation reaction of [Cu(NMe2-TMPA)] formation of the superoxo compound occurs within the mixing timescale, and peroxo formation is delayed for two reasons 1) the equilibrium is considerably larger than for R = MeO and H, and 2) the rapid rate (according to k- depletes Cu as most of it is bound as Cu -... 

Figure 14.17 Structures of (a) the tetraperoxochromate(V) ion [Cr (02)4] , (b) the pyridine oxodiperoxo-chromium(VI) complex [Cr 0(02)2py], and (c) the triamminodiperoxochromium(IV) complex [Cr" (NH3)3(02)2] showing important interatomic distances and angles. (This last compound was originally described as a chromium(II) superoxo complex [Ci (NH3)3(02)2] on the basis of an apparent 0-0 distance of 131 pm/ and is a salutary example of the factual and interpretative errors that can arise even in X-ray diffraction studies. " ...

Reactivity of compounds 1 and 2c with O2 is remarkably different from that of 5c, 5cCo, and 8 (Fig. 18.18). Metalloporphyrin 2c binds O2 reversibly at room temperature under anhydrous conditions to produce a diamagnetic ferric-superoxo/Cu adduct as demonstrated by resonance Raman spectroscopy using 2 and 2... 

Compound 1 (Fig. 18.18) reversibly forms an analogous ferric-superoxo/Cu adduct at 60 °C, as demonstrated by resonance Raman spectroscopy. However, warming the sample to 40 °C results in a rapid four-electron reduction of the bound O2 ligand, generating a ferryl/Cu /phenoxyl radical derivative (Fig. 18.18) [Collman et al., 2007a]. 

The complexes [LCo(p-02)(p-OH)CoL] [L = en, trien, dien, tetra-ethylenepentamine, or tris-(2-aminoethyl)amine] have been studied, and the new complexes [[Co(imidazole)(gly)2 202],4H20 [ Co2(imidazole)2-(gly)402 0H],3H20, and [Co(imidazole)(gly)2(02)H20] have been prepared The spectroscopic properties of various p-peroxo- and p-superoxo-cobalt(iii) complexes have been examined. The singly-bridged p-peroxo-compounds have a strong band at 300 nm, whereas this falls at 350 nm for p-peroxo-p-hydroxo-complexes and two peaks at 480 and 700 nm are observed for p-superoxo-species. The i.r. spectra of p-peroxo-bridged complexes of cobalt(iii)-cyclam have been reported. ... 

The structure of the active component, manganese pyrophosphate, has been reported in the literature (24). It is layer like with planes of octahedrally coordinated Hn ions being separated by planes of pyrophosphate anions (P20y ). Examination of models of this compound gave calculated Hn-Hn thru space distances of 3.26 and 3.45 angstroms, a metal-metal distance close to that found for binuclear dibridged peroxo- and superoxo- complexes of cobalt ( ). 

While most superoxo complexes—in contrast to peroxo compounds— have been assigned a bent, end-on coordination mode [9], the superoxide ligand of Tp Cr(02)Ph was suggested to exhibit the more unusual side-on (r] ) coordination [10]. The reactivity of the complex did not allow for the determination of its molecular structure however, close analogs could be isolated, crystallized and structurally characterized by X-ray diffraction. For example, the reaction of [Tp Cr(pz H)]BARF (pz H = 3-tert-butyl-5-methylpyrazole, BARF = tetrakis(3,5-bis(trifiuoromethyl)phenyl)borate) with O2 produced the stable dioxygen complex [Tp Cr(pz H)( ] -02)]BARF (Scheme 3, bottom), which featured a side-on bound superoxide ligand (do-o = 1.327(5) A, vo-o = 1072 cm ) [11]. Other structurally characterized... 

The UV spectral data for several hydroperoxo complexes in aqueous solution are shown in Table II. Intense transitions appear for all the compounds at wavelengths that are well below the 270-290 nm maxima for the superoxo complexes. This feature is particularly useful in mechanistic studies of the complex reactions involving several forms of activated oxygen simultaneously (58). 

Nishinaga and co-workers isolated a series of stable cobalt(III)-alkyl peroxide complexes such as (170) and (171) in high yields from the reaction of the pentacoordinated Co"-Schiff base complex with the corresponding phenol and 02 in CH2C12. Complex (170 R=Bu ) has been characterized by an X-ray structure. These alkyl peroxide complexes presumably result from the homolytic addition of the superoxo complex Co111—02 to the phenoxide radical obtained by hydrogen abstraction from the phenolic substrate by the CoUI-superoxo complex. The quinone product results from / -hydride elimination from the alkyl peroxide complex (172)561,56,565,566 The quinol (169) produced by equation (245) has been shown to result from the reduction of the CoIU-alkyl peroxide complex (170) by the solvent alcohol which is transformed into the corresponding carbonyl compound (equation 248).561... 

Of greatest interest are those compounds that attempt to model hemoglobin directly. Simple iron(II) porphyrins are readily autoxidized first to superoxo species, then to //-peroxo dimers and finally to /x-oxo dimers, as represented in equation (60). Bridge formation must be prevented if carrier properties are to be observed. This has been achieved by the use of low temperature and sterically hindered or immobilized iron(II) porphyrins. Irreversible oxidation is also hindered by the use of hydrophobic environments. In addition, model porphyrins should be five-coordinate to allow the ready binding of 02 this requires that one side should be protected with a hydrophobic structure. Attempts have also been made to investigate the cooperative effect by studying models in which different degrees of strain have been introduced. 

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