Arsenite
Chemical compounds containing arsenic at oxidation state +3
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A number of different arsenite anions are known:
- AsO3−3 orthoarsenite, an ion of arsenous acid, with a pyramidal shape
- (AsO−2)n metaarsenite, a polymeric chain anion.
- As2O4−5 pyroarsenite, [O2As−O−AsO2]4−
- As3O5−7 catena-triarsenite, [O2As−O−As(O)−O−AsO2]5−
- As4O6−9 catena-tetraarsenite, [O2As−O−As(O)−O−As(O)−O−AsO2]6−
- As4O4−8 cyclo-tetraarsenite
- (As6O4−11)n, a polymeric anion
In all of these the geometry around the AsIII centers are approximately trigonal, the lone pair on the arsenic atom is stereochemically active. Well known examples of arsenites include sodium metaarsenite which contains a polymeric linear anion, (AsO−2)n, and silver orthoarsenite, Ag3AsO3, which contains the trigonal AsO3−3 anion.
Preparation of arsenites
Some arsenite salts can be prepared from an aqueous solution of As2O3. Examples of these are the metaarsenite salts and at low temperature, hydrogen arsenite salts can be prepared, such as Na2H2As4O8, NaAsO2·4H2O, Na2HAsO3·5H2O and Na5(HAsO3)(AsO3)·12H2O.
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Arsenite minerals
A number of minerals contain arsenite anions: reinerite, Zn3(AsO3)2; finnemanite, Pb5Cl(AsO3)3; paulmooreite, Pb2As2O5; stenhuggarite, CaFeSbAs2O7 (contains a complex polymeric anion); schneiderhöhnite, FeII
FeIII
3(AsO3)(As2O5)2; magnussonite, Mn5(OH)(AsO3)3; trippkeite, CuAs2O4; trigonite, Pb3Mn(AsO3)2(HAsO3); tooeleite, Fe6(AsO3)4(SO4)(OH)4·4H2O.
Arsenites in the environment
Arsenic can enter groundwater due to naturally occurring arsenic at deeper levels or from mine workings. Arsenic(III) can be removed from water by a number of methods, oxidation of As(III) to As(V) for example with chlorine followed by coagulation with for example iron(III) sulfate. Other methods include ion-exchange and filtration. Filtration is only effective if arsenic is present as particulates, if the arsenite is in solution it passes through the filtration membrane.
Uses
Sodium arsenite is used in the water gas shift reaction to remove carbon dioxide. Fowler's solution first introduced in the 18th century was made up from As2O3 as a solution of potassium metaarsenite, KAsO2.
Arsenic in its trioxide, As2O3, (brand name Trisenox, ATO) is used as a chemotherapy drug against acute promyelocytic leukaemia (APL), a type of myeloid leukemia. The detailed mechanism of action is unknown, but it is suspected to speed up apoptosis of cancer cells. Arsenic trioxide triggers morphological changes and DNA fragmentations in NB4 in vitro model for APL. It also degrades retinoic acid receptor alpha (RARA). RARA gene is important regulator of premyelocytic immune cell development, differentiation, and apoptosis.
Bacteria using and generating arsenite
Some species of bacteria obtain their energy by oxidizing various fuels while reducing arsenates to form arsenites. The enzymes involved are known as arsenate reductases.
In 2008, bacteria were discovered that employ a version of photosynthesis with arsenites as electron donors, producing arsenates (just like ordinary photosynthesis uses water as electron donor, producing molecular oxygen). The researchers conjectured that historically these photosynthesizing organisms produced the arsenates that allowed the arsenate-reducing bacteria to thrive.
In humans, arsenite inhibits pyruvate dehydrogenase (PDH complex) in the pyruvate-acetyl CoA reaction, by binding to the –SH group of lipoamide, a participant coenzyme. It also inhibits the oxoglutarate dehydrogenase complex by the same mechanism. The inhibition of these enzymes disrupts energy production.