Transition metal formyl complex explained

In organometallic chemistry, a transition metal formyl complex is a metal complex containing one (usually) or more formyl (CHO) ligand. A subset of transition metal acyl complexes, formyl complexes can be viewed as metalla-aldehydes. A representative example is (CO)5ReCHO. The formyl is viewed as an X (pseudohalide) ligand. Metal formyls are proposed as intermediates in the hydrogenation of carbon monoxide, as occurs in the Fischer-Tropsch process.[1]

Structure and bonding

The MCHO group is planar. A C=O double bond is indicated by X-ray crystallography. A second resonance structure has a M=C double bond, with negative charge on oxygen.

Synthesis and reactions

Metal formyl complexes are often prepared by the reaction of metal carbonyls with hydride reagents:[2]

[Re(CO)<sub>6</sub>]+ + H → (CO)5ReCHOThe CO ligand is the electrophile and the hydride (provided typically from a borohydride) is the nucleophile.

Some metal formyls are produced by reaction of metal carbonyl anions with reagents that donate the equivalent of a formyl cation, such a mixed formate anhydrides.[3]

Metal formyls participate in many reactions, many of which are motivated by interest in Fischer-Tropsch chemistry. O-alkylation gives carbenoid complexes. The formyl ligand also functions as a base, allowing the formation of M-CH=O-M' linkages.[4] Decarbonylation leads to de-insertion of the carbonyl, yielding hydride complexes.[1]

References

  1. Book: 10.1016/S0065-3055(08)60519-5. Transition Metal Formyl Complexes. Advances in Organometallic Chemistry. 1982. Gladysz. J.A.. 20. 1–38. 9780120311200.
  2. 10.1021/acs.chemrev.6b00034. Main Group Lewis Acid-Mediated Transformations of Transition-Metal Hydride Complexes. 2016. Maity. Ayan. Teets. Thomas S.. Chemical Reviews. 116. 15. 8873–8911. 27164024.
  3. 10.1021/ja00793a066. Isolation and Characterization of a Kinetically Stable transition Metal Formyl complex. 1973. Collman. J. P.. Winter. S. R.. Journal of the American Chemical Society. 95. 12. 4089–4090.
  4. 10.1039/b414943b. Insertion Reactions of Hydridonitrosyltetrakis(trimethylphosphine) Tungsten(0). 2005. Chen. Zilu. Schmalle. Helmut W.. Fox. Thomas. Berke. Heinz. Dalton Transactions. 3. 580–587. 15672204.