Structure and reactivity of a mononuclear non-haem iron(III)-peroxo complex

Oxygen-containing mononuclear iron species--iron(III)-peroxo, iron(III)-hydroperoxo and iron(IV)-oxo--are key intermediates in the catalytic activation of dioxygen by iron-containing metalloenzymes. It has been difficult to generate synthetic analogues of these three active iron-oxygen species in identical host complexes, which is necessary to elucidate changes to the structure of the iron centre during catalysis and the factors that control their chemical reactivities with substrates. Here we report the high-resolution crystal structure of a mononuclear non-haem side-on iron(III)-peroxo complex, [Fe(III)(TMC)(OO)](+). We also report a series of chemical reactions in which this iron(III)-peroxo complex is cleanly converted to the iron(III)-hydroperoxo complex, [Fe(III)(TMC)(OOH)](2+), via a short-lived intermediate on protonation. This iron(III)-hydroperoxo complex then cleanly converts to the ferryl complex, [Fe(IV)(TMC)(O)](2+), via homolytic O-O bond cleavage of the iron(III)-hydroperoxo species. All three of these iron species--the three most biologically relevant iron-oxygen intermediates--have been spectroscopically characterized; we note that they have been obtained using a simple macrocyclic ligand. We have performed relative reactivity studies on these three iron species which reveal that the iron(III)-hydroperoxo complex is the most reactive of the three in the deformylation of aldehydes and that it has a similar reactivity to the iron(IV)-oxo complex in C-H bond activation of alkylaromatics. These reactivity results demonstrate that iron(III)-hydroperoxo species are viable oxidants in both nucleophilic and electrophilic reactions by iron-containing enzymes.     

New Polypheretima and Pithemera (Oligochaeta: Megascolecidae) species from the Mt. Malindang Range,Mindanao Island,Philippines

We describe four new pheretimoid earthworm species, one in Polypheretima and three in Pithemera, from Mt. Malindang, Misamis Occidental Province, Mindanao Island, Philippines, and provide diagrams of external morphology and internal anatomy. Polypheretima mindanaoensis sp. nov. belongs to the Po. elongata species group, characterised by having genital markings on xix and successive segments and pairs of spermathecal batteries in vi and/or vii. It differs from the other members of the Po. elongata species group in having no copulatory bursae. This species shows individual variation in the number of spermathecae in each battery. Individuals that lack spermathecae are presumed to reproduce parthenogenetically. Pithemera malindangensis sp. nov. and Pi. duminagati sp. nov. belong to the Pi. bicincta species group, characterised by having the first spermathecal pores in 4/5. These two species differ in size and in the distance between male pores. Pithemera donvictorianoi sp. nov. belongs to the Pi. pacifica species group, characterised by having the first spermathecal pores in 5/6. This is the only member of this species group so far reported from the Philippines, and this is the only Philippine Pithemera species whose clitellum covers two rather than two and a half segments. Current studies show that worldwide, the Philippines has the highest diversity for Pithemera, with 13 species, followed by Papua New Guinea and the Pacific Islands, each area with six species. Indonesia has the highest diversity for Polypheretima, with 18 species, followed by Vietnam with 13 species, and then Papua New Guinea and the Philippines, each area with eight species. These findings indicate a high degree of endemicity within these areas, suggesting that many species remain to be detected in the Philippines.

http://zoobank.org/urn:lsid:zoobank.org:pub:2198709C-F5E1-4A0D-A185-CA506D206171