Transition metal nitrite complex

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Sodium cobaltinitrite is a salt of the coordination complex [Co(NO2)6]3−.[1]

In

ligands.[2] Although the synthetic derivatives are only of scholarly interest, metal-nitrite complexes occur in several enzymes that participate in the nitrogen cycle.[3]

Structure and bonding

[Co(NH3)5(NO2)]2+

Bonding modes

Three

linkage isomers are common for nitrite ligands, O-bonded, N-bonded, and bidentate O,O-bonded. The former two isomers have been characterized for the pentamminecobalt(III) system, i.e. [(NH3)5Co−NO2]2+ and [(NH3)5Co−ONO]2+, referred to as N-nitrito and O-nitrito, respectively. These two forms are sometimes called nitro and nitrito. These isomers can be interconverted in some complexes.[4]

An example of chelating nitrite is [Cu(bipy)2(O2N)]NO3 – "bipy" is the

bidentate ligand 2,2′-bipyridyl
. This bonding mode is sometimes described as κ2O,O-NO2.

Focusing on electron-counting in monometallic complexes, O-bonded, N-bonded are viewed as 1-electron pseudohalides ("X-ligand"). The bidentate O,O-bonded is an "L-X ligand", akin to bidentate carboxylate.

With respect to HSAB theory, the N bonding mode is more common for softer metal centers. The O and O,O-bidentate modes are hard ligands, being found on Lewis-acidic metal centers.

The kinetically-favored O-bonded isomer [(NH3)5Co−ONO]2+ converts to [(NH3)5Co−NO2]2+. In its reaction with ferric porphyrin complexes, nitrite gives the O-bonded isomer, Fe(porph)ONO. Addition of donor ligands to this complex induces the conversion to the octahedral low-spin isomer, which now is a soft Lewis acid. The nitrite isomerizes to the N-bonded isomer, Fe(porph)NO2(L).[5]

The isomerization of [(NH3)5Co−ONO]2+ to [(NH3)5Co−NO2]2+ proceeds in an intramolecular manner.[6]

Homoleptic complexes

[Cd(NO2)4]2− center as occurs as the dipotassium salt (color code: red (O), blue (N)).

Several homoleptic (complexes with only one kind of ligand) complexes have been characterized by

Co, Rh).[7][8] Square-planar homoleptic complexes are also known for Pt(II) and Pd(II). The potassium salts of [M(NO2)4]2− (M = Zn, Cd) feature homoleptic complexes with four O,O-bidentate nitrite ligands.[9]

Synthesis of nitrito complexes

Traditionally metal nitrito complexes are prepared by

salt metathesis or ligand substitution reactions using alkali metal nitrite salts, such as sodium nitrite. At neutral pH, nitrite exists predominantly as the anion, not nitrous acid.[10]

Metal nitrosyl complexes undergo base hydrolysis, yielding nitrite complexes. This pattern is manifested in the behavior of

nitroprusside
:

[Fe(CN)5NO]2− + 2 OH− → [Fe(CN)5NO2]4− + H2O

Reactions of nitrito complexes

Some anionic nitrito complexes undergo acid-induced deoxygenation to give the

nitrosyl complex.[11]

[LnMNO2]− + H+ → [LnMNO]+ + OH−

The reaction is reversible in some cases. Thus, one can generate nitrito complexes by base-hydrolysis of electrophilic metal nitrosyls.

Nitro complexes also catalyze the oxidation of alkenes.[12]

Bioinorganic chemistry

Metal nitrito complexes figure prominently in the nitrogen cycle, which describes the relationships and interconversions of ammonia up to nitrate. Because nitrogen is often a limiting nutrient, this cycle is important. Nitrite itself does not readily undergo redox reactions, but its metal complexes do.[13]

Oxidation to nitrate

The molybdenum-containing enzyme nitrite oxidoreductase catalyzes the oxidation of nitrite to nitrate:

NO−2 + H2O → NO−3 + 2 H+

Reduction

The heme-based enzyme nitrite reductase catalyzes the conversion of nitrite to ammonia. The cycle begins with reduction of an iron-nitrite complex to a metal nitrosyl complex.[3]

The copper-containing enzyme

isonitrosyl
).

References

  1. ISBN 978-0-08-037941-8
    .
  2. doi:10.1016/S0010-8545(00)80527-5
    .
  3. ^
    PMID 26158348
    .
  4. PMID 19863116
    .
  5. PMID 20666383
    .
  6. doi:10.1021/ic50206a022
    .
  7. doi:10.1107/S0108768195016879
    .
  8. doi:10.1107/S0108270193011588
    .
  9. doi:10.1107/S0108270187096471
    .
  10. ISBN 9780470132395
    .
  11. ISBN 978-0-08-037941-8
    .
  12. PMID 26211412
    .
  13. PMID 24694090
    .
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