Radicals complexes

Reaction 36 may occur through a peroxy radical complex with the metal ion (2,25,182). In any event, reaction 34 followed by reaction 36 is the equivalent of a metal ion-cataly2ed hydrogen abstraction by a peroxy radical. 

N—Fe(IV)Por complexes. Oxo iron(IV) porphyrin cation radical complexes, [O—Fe(IV)Por ], are important intermediates in oxygen atom transfer reactions. Compound I of the enzymes catalase and peroxidase have this formulation, as does the active intermediate in the catalytic cycle of cytochrome P Q. Similar intermediates are invoked in the extensively investigated hydroxylations and epoxidations of hydrocarbon substrates cataly2ed by iron porphyrins in the presence of such oxidizing agents as iodosylbenzene, NaOCl, peroxides, and air. 

In many cases, however, the ortho isomer is the predominant product, and it is the meta para ratio which is close to the statistical value, in reactions both on benzenoid compounds and on pyri-dine. " There has been no satisfactory explanation of this feature of the reaction. One theory, which lacks verification, is that the radical first forms a complex with the aromatic compound at the position of greatest electron density that this is invariably cither the substituent or the position ortho to the substituent, depending on whether the substituent is electron-attracting or -releasing and that when the preliminary complex collapses to the tr-complex, the new bond is most likely to be formed at the ortho position.For heterocyclic compounds such as pyridine it is possible that the phenyl radical complexes with the nitrogen atom and that a simple electronic reorganization forms the tj-complex at the 2-position. 

Fig. 3. Proposed routes for conversion of the peroxo intermediate to intermediate Q, one involving loss of water (left-hand side) and one not (right-hand side). In the former case the resulting diiron(IV) oxo species could bind an oxygen atom with one iron, or the oxygen could be bound symmetrically by both iron atoms. Although written as an iron(IV) oxo species, Q can also be formulated as an iron(III) oxyl radical complex (35,51).

A 5 day old sample of the crystalline radical complex exploded violently on agitation. 

The active enzyme abstracts a hydrogen atom stereospecifically from the intervening methylene group of a PUFA in a rate-limiting step, with the iron being reduced to Fe(II). The enzyme-alkyl radical complex is then oxidized by molecular oxygen to an enzyme-peroxy radical complex under aerobic conditions, before the electron is transferred from the ferrous atom to the peroxy group. Protonation and dissociation from... 

We are therefore faced here with radical complexes which easily distort depending on the structural arrangement and whose SOMO is different for every crystal structure associated with a given counter-ion, a very original feature in these series. The unfolded d1 complexes can be described as Mo(IV) complexes with a spin density essentially localized on the dithiolene ligand while the more folded complexes have a stronger metal character. This variable spin density delocalization is expected to influence strongly the amplitude and dimensionality of intermolecular interactions between radical species in the solid state, as detailed below in Sect. 3. 

CpMo(S2C2Ph2)2] at 2.0275, 2.0074 and 1.9936 or from oriented single-crystal for [Cp Mo(dmit)2] at 2.027, 2.012 and 1.992, demonstrate an extensive delocalization of the unpaired electron the dithiolene ligands. The solid state properties of these series of radical complexes will be described below in detail in Sect. 3. 

As mentioned above for the [Cp2Mo(dithiolene)]+, the [Cp Mo(dithiolene)2] and the [CpNi(dithiolene)] radical complexes, the spin density is not only partially delocalized on the dithiolene ligand but also on the metal and even the Cp rings. This peculiar feature opens new paths for intermolecular interactions in the solid state besides the direct dithiolene/dithiolene overlaps, since Cp/dithiolene and Cp/Cp contacts are also to be considered. 

A three-dimensional set of intermolecular interactions is further confirmed by the observation of a transition to an antiferromagnetic ground state in both radical complexes, at a Neel temperatures of 8 (Mo) and 4.5 K (W), in accordance with the difference of Curie-Weiss temperatures between both complexes. Note also the spin-flop field in the antiferromagnetic state, found at 5.5 kG in [Cp M(dmit)2] and at 8 kG in [Cp W(dmit)2] , a consequence of the stronger spin orbit coupling in the latter. 

Interesting earlier work on uncoordinated phenoxyl radical complexes shown in Fig. 10 has been reported by Medzhidov and co-workers (138-141) who synthe-... 

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