Transition metal nitroso complexes explained

Transition metal nitroso complexes are coordination complexes containing one or more organonitroso ligands (RNO).[1]

Structure and bonding

thumb|right|Structure of the dye Naphthol Green B, which features of nitroso ligand bound to Fe(III).Organic nitroso compounds bind to metals in several ways, but most commonly as monodentate N-bonded ligands. Also known are O-bonded, η2-N,O-bonded. Dimers of organic nitroso compounds also bind in a κ2--O,O bidentate manner.

Synthesis

Organic nitroso complexes can be prepared from preformed organic nitroso precursors. These precursors usually exist as N-N bonded dimers, but the dimer dissociates readily. This direct method is used to give W(CO)5(tert-BuNO) (where tert-Bu is).[2] The Fe-porphyrin complex depicted below is prepared by this route. More complicated but more biorelevant routes involve degradation of precursors such as nitrobenzene and phenylhydroxylamine.[3]

(Et = C2H5, i-Pr = (CH3)2CH)

The coupling of organic ligands and nitric oxide is yet another route.[1]

Connection to methemoglobinemia

Methemoglobinemia is a disorder where a large fraction of hemoglobin in one's blood has converted to inactive forms, generically called methemoglobin. Since methemoglobin is not an oxygen-carrier, methemoglobinemia is a serious disorder, sometimes fatal. Exposure to nitrobenzene, aniline, and their derivatives cause this disorder, which is attributed to their conversion to nitrosobenzene (and derivatives), which inactivate hemoglobin by forming a complex with the Fe center, precluding binding of O2.[4]

References

  1. 10.1021/cr0000731 . Interactions of Organic Nitroso Compounds with Metals . 2002 . Lee . Jonghyuk . Chen . Li . West . Ann H. . Richter-Addo . George B. . Chemical Reviews . 102 . 4 . 1019–1066 . 11942786 .
  2. Pilato . R. S. . McGettigan . C. . Geoffroy . G. L. . Rheingold . A. L.. Geib . S. J. . tert-Butylnitroso Complexes. Structural Characterization of W(CO)5(N(O)Bu-tert) and [CpFe(CO)(PPh<sub>3</sub>)(N(O)Bu-''tert'')]+ . Organometallics . 1990 . 9 . 2 . 312–17 . 10.1021/om00116a004.
  3. 10.1021/ic50203a050 . Kinetics and Mechanism of Oxygen Atom Transfer from Nitro Compounds Mediated by Nickel(0) Complexes . 1980 . Berman . R. S. . Kochi . J. K. . Inorganic Chemistry . 19 . 248–254 .
  4. 10.1021/ja9832820 . Solid-State NMR, Mössbauer, Crystallographic, and Density Functional Theory Investigation of Fe−O2and Fe−O2Analogue Metalloporphyrins and Metalloproteins . 1999 . Godbout . Nathalie . Sanders . Lori K. . Salzmann . Renzo . Havlin . Robert H. . Wojdelski . Mark . Oldfield . Eric . Journal of the American Chemical Society . 121 . 16 . 3829–3844 .