Metal carbonyl hydride

Cobalt tetracarbonyl hydride

Metal carbonyl hydrides are complexes of transition metals with carbon monoxide and hydride as ligands. These complexes are useful in organic synthesis as catalysts in homogeneous catalysis, such as hydroformylation.

Preparation

Walter Hieber prepared the first metal carbonyl hydride in 1931 by the so-called Hieber base reaction of metal carbonyls. In this reaction a hydroxide ion reacts with the carbon monoxide ligand of a metal carbonyl such as iron pentacarbonyl in a nucleophilic attack to form a metallacarboxylic acid. This intermedia releases of carbon dioxide in a second step, giving the iron tetracarbonyl hydride anion. The synthesis of cobalt tetracarbonyl hydride (HCo(CO)₄) proceeds in the same way.^[1]

Fe(CO)₅ + NaOH → Na[Fe(CO)₄CO₂H]

Na[Fe(CO)₄CO₂H] → Na[HFe(CO)₄] + CO₂

A further synthetic route is the reaction of the metal carbonyl with hydrogen.^[2] The protonation of metal carbonyl anions, e.g. [Co(CO)₄]^-, leads also to the formation of metal carbonyl hydrides.

Properties

Metal Carbonyl hydride	pKa
HCo(CO)4	"strong"
HCo(CO)3(P(OPh)3)	5.0
HCo(CO)3(PPh3)	7.0
HMn(CO)5	7.1
H2Fe(CO)4	4.4, 14
[HCo(dmgH)2PBu3]	10.5

The neutral metal carbonyl hydrides are often volatile and can be quite acidic.^[3] The hydrogen atom is directly bounded to the metal. The metal-hydrogen bond length is for cobalt 114 pm, the metal-carbon bond length is for axial ligands 176  and 182  for the equatorial ligands.^[4]

Applications

Metal carbonyl hydride are used as catalysts in the hydroformylation of olefins. Under industrial conditions the catalyst is usually formed in situ in a reaction of a metal salt precursor with the syngas. The hydroformylation starts with the generation of a coordinatively unsaturated 16-electron metal carbonyl hydride complex like HCo(CO)₃ or HRh(CO)(PPh₃)₂ by dissociation of a ligand. Such complexes bind olefins in a first step via π-complexation. In a second step an alkyl complex is formed by insertion of the olefin into the metal-hydrogen bond, leading once again to a 16-electron species. This complex can bind another carbon monoxide, which can insert into the metal-carbon bond of the alkyl ligand to form an acyl complex. By oxidative addition of hydrogen and elimination of the aldehyde the initial metal carbonyl hydride complex is regenerated.

Analytical characterization

It has been uncertain for a long time whether metal carbonyl hydrides contain a direct metal-hydrogen bond, although this has been suspected by Hieber for H₂Fe(CO)₄. The precise structure cannot be identified by X-ray diffraction, particularly the length of a possible metal-hydrogen bond remained uncertain.^[5] The exact structure of the metal carbonyl hydrides has been determined by using neutron diffraction and nuclear magnetic resonance spectroscopy.^[4][6]

Further reading

• Holleman, A. F.; Wiberg, E. (2001), Inorganic Chemistry, San Diego: Academic Press, ISBN 0-12-352651-5

References

1. W. Hieber, F. Leutert: Zur Kenntnis des koordinativ gebundenen Kohlenoxyds: Bildung von Eisencarbonylwasserstoff. Die Naturwissenschaften. volume 19, 1931, pp. 360–361, doi:10.1007/BF01522286.
2. H. D. Kaesz,R. B. Saillant: Hydride Complexes of the Transition Metals" Chem. Rev., 1972, volume 72, pp 231–281.doi:10.1021/cr60277a003.
3. Ralph G. Pearson The transition-metal-hydrogen bond. Chemical Reviews. volume 85, 1985, S. 41–49, doi:10.1021/cr00065a002.
4. E. A. McNeill, F. R. Scholer: Molecular structure of the gaseous metal carbonyl hydrides of manganese, iron, and cobalt. Journal of the American Chemical Society. volume 99, 1977, S. 6243–6249, doi:10.1021/ja00461a011.
5. F. A. Cotton: Structure and Bonding in Metal Carbonyls and Related Compounds. In: Helvetica Chimica Acta. 50, 1967, S. 117–130, doi:10.1002/hlca.19670500910.
6. Bau, R.; Drabnis, M. H., "Structures of transition metal hydrides determined by neutron diffraction", Inorg. Chim. Acta 1997, 259, 27-50. doi:10.1016/S0020-1693(97)89125-6

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