Transition metal oxo complex
![](http://upload.wikimedia.org/wikipedia/commons/thumb/1/14/Bridging%26terminal_oxo_ligands.png/200px-Bridging%26terminal_oxo_ligands.png)
A transition metal oxo complex is a
Reactivity
Olation and acid-base reactions
A common reaction exhibited by metal-oxo compounds is
Oxygen-atom transfer
Metal oxo complexes are intermediates in many metal-catalyzed oxidation reactions. Oxygen-atom transfer is common reaction of particular interest in organic chemistry and biochemistry.[3] Some metal-oxos are capable of transferring their oxo ligand to organic substrates. One such example of this type of reactivity is from and enzyme superfamily Molybdenum oxotransferase.
In water oxidation catalysis, metal oxo complexes are intermediates in the conversion of water to O2.
Hydrogen-atom abstraction
Transition metal-oxo's are also capable of abstracting strong C–H, N–H, and O–H bonds. Cytochrome P450 contains a high-valent iron-oxo which is capable of abstracting hydrogen atoms from strong C–H bonds.[4]
Molecular oxides
Some of the longest known and most widely used oxo compounds are oxidizing agents such as
- vanadyl chloride (d0), a tungsten oxo carbonyl (d2), permanganate (d0), [ReO2(pyridine)4]+ (d2), simplified view of compound I (a state of cytochrome P450, d4), and Ir(O)(mesityl)3 (d4).[7]
Metalloenzymes
Iron(IV)-oxo species
![](http://upload.wikimedia.org/wikipedia/commons/thumb/8/85/CYP_mechanism.png/220px-CYP_mechanism.png)
Iron(IV)-oxo compounds are intermediates in many biological oxidations:
- ketoglutarate, generating Fe(IV)=O centers, i.e. ferryl, that hydroxylate a variety of hydrocarbon substrates.[9]
- Cytochrome P450 enzymes, use a heme cofactor, insert ferryl oxygen into saturated C–H bonds,[10] epoxidize olefins,[11][12] and oxidize aromatic groups.[13]
- Methane monooxygenase (MMO) oxidizes methane to methanol via oxygen atom transfer from an iron-oxo intermediate at its non-heme diiron center.[14] Much effort is aimed at reproducing reactions with synthetic catalysts.[6]
Molybdenum/tungsten oxo species
The oxo ligand (or analogous sulfido ligand) is nearly ubiquitous in molybdenum and tungsten chemistry, appearing in the ores containing these elements, throughout their synthetic chemistry, and also in their biological role (aside from nitrogenase). The biologically transported species and starting point for biosynthesis is generally accepted to be oxometallates MoO4−2 or WO4−2. All Mo/W enzymes, again except nitrogenase, are bound to one or more molybdopterin prosthetic group. The Mo/W centers generally cycle between hexavalent (M(VI)) and tetravalent (M(IV)) states. Although there is some variation among these enzymes, members from all three families involve oxygen atom transfer between the Mo/W center and the substrate.[15] Representative reactions from each of the three structural classes are:
- Sulfite oxidase: SO3−2 + H2O → SO4−2 + 2 H+ + 2 e−
- DMSO reductase: H3CS(O)CH3 (DMSO) + 2 H+ + 2 e− → H3CSCH3 (DMS) + H2O
- Aldehyde ferredoxin oxidoreductase: RCHO + H2O → RCO2H + 2 H+ + 2 e−
The three different classes of molybdenum cofactors are shown in the Figure. The biological use of tungsten mirrors that of molybdenum.[16]
Oxygen-evolving complex
The active site for the oxygen-evolving complex (OEC) of photosystem II (PSII) is a Mn4O5Ca centre with several bridging oxo ligands that participate in the oxidation of water to molecular oxygen.[17] The OEC is proposed to utilize a terminal oxo intermediate as a part of the water oxidation reaction. This complex is responsible for the production of nearly all of earth's molecular oxygen. This key link in the oxygen cycle is necessary for much of the biodiversity present on earth.
![](http://upload.wikimedia.org/wikipedia/commons/thumb/e/ef/Oxygen_Evolving_Complex_Crystal_structure_to_1.9_Angstrom_Resolution.png/220px-Oxygen_Evolving_Complex_Crystal_structure_to_1.9_Angstrom_Resolution.png)
The "oxo wall"
![](http://upload.wikimedia.org/wikipedia/en/thumb/3/37/Metal-oxo_MO_%28d0%29.png/300px-Metal-oxo_MO_%28d0%29.png)
The term "oxo wall" is a theory used to describe the fact that no terminal oxo complexes are known for metal centers with octahedral symmetry and d-electron counts beyond 5.[18][19]
Oxo compounds for the vanadium through iron triads (Groups 3-8) are well known, whereas terminal oxo compounds for metals in the cobalt through zinc triads (Groups 9-12) are rare and invariably feature metals with coordination numbers lower than 6. This trend holds for other metal-ligand multiple bonds. Claimed exceptions to this rule[20][21][22] have been retracted.[23][24][25]
The iridium oxo complex Ir(O)(mesityl)3 may appear to be an exception to the oxo-wall, but it is not because the complex is non-octahedral.[7] The trigonal symmetry reorders the metal d-orbitals below the degenerate MO π* pair. In three-fold symmetric complexes, multiple MO bonding is allowed for as many as 7 d-electrons.[18]
Terminal oxo ligands are also rather rare for the titanium triad, especially zirconium and hafnium and are unknown for group 3 metals (scandium, yttrium, and lanthanum).[1]
See also
- Metal-ligand multiple bond
- Oxide
- Polyoxometalate
- Metallate
- Oxophilic
- Dioxygen complex
References
- ^ a b c d Nugent, W. A., Mayer, J. M. "Metal-Ligand Multiple Bonds." John Wiley & Sons, New York, 1988.
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- ^ Ritter, Stephen K. (June 12, 2012). "Metal-Oxo Papers Retracted". cen.acs.org. Retrieved 2021-05-15.
- ^ Hadlington2012-06-14T00:00:00+01:00, Simon. "Oxo wall still stands as inorganic papers retracted". Chemistry World. Retrieved 2021-05-15.
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