Metal carbonyl hydride

A commercially important rhodium carbonyl 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.[1]

Preparation

Main article: metal hydride complex

Decacarbonyldihydridotriosmium is one of many polymetallic carbonyl hydrides.

Walter Hieber et al. 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.[2]

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.[3] The protonation of metal carbonyl anions, e.g. [Co(CO)₄]^−, leads also to the formation of metal carbonyl hydrides.

Properties

Some Metal Carbonyl Hydrides

Metal Carbonyl hydride	pKa
HCo(CO)4	1[4]
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
HRh(CO)(PPh3)3	unknown

The neutral metal carbonyl hydrides are often volatile and can be quite acidic.[5] 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.[6]

A direct metal-hydrogen bond was suspected by Hieber for H₂Fe(CO)₄. A number of metal carbonyl hydrides have been characterized by X-ray crystallography[7] and neutron diffraction.[6][8] Nuclear magnetic resonance spectroscopy has also proved to be a useful characterization tool.

Applications and occurrence

Metal carbonyl hydrides are used as catalysts in the hydroformylation of olefins. 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, thus beginning the transformation of the alkene to the aldehyde.

Iron carbonyl hydrides occur in nature at the active sites of hydrogenase enzymes.[9]

Further reading

• Holleman, Arnold Frederik; Wiberg, Egon (2001), Wiberg, Nils (ed.), Inorganic Chemistry, translated by Eagleson, Mary; Brewer, William, San Diego/Berlin: Academic Press/De Gruyter, ISBN 0-12-352651-5

References

1. J. F. Hartwig; Organotransition metal chemistry - from bonding to catalysis. University Science Books. 2009. 753, 757-578. ISBN 978-1-891-38953-5.
2. Hieber, W.; Leutert, F. (1931). "Zur Kenntnis des koordinativ gebundenen Kohlenoxyds: Bildung von Eisencarbonylwasserstoff". Die Naturwissenschaften. 19 (17): 360–361. Bibcode:1931NW.....19..360H. doi:10.1007/BF01522286. S2CID 791569.
3. Kaesz, H. D.; Saillant, R. B. (1972). "Hydride complexes of the transition metals". Chemical Reviews. 72 (3): 231–281. doi:10.1021/cr60277a003.
4. Holleman, Arnold F.; Wiberg, Egon; Wiberg, Nils (1995). Lehrbuch der anorganischen Chemie (in German). Berlin. ISBN 978-3-11-012641-9. OCLC 237142268.
5. Ralph G. Pearson. "The Transition-Metal-Hydrogen Bond". Chemical Reviews. 85: 1985. doi:10.1021/cr00065a002.
6. McNeill, E. A.; Scholer, F. R. (1977). "Molecular Structure of the Gaseous Metal Carbonyl Hydrides of Manganese, Iron, and Cobalt". Journal of the American Chemical Society. 99 (19): 6243–6249. doi:10.1021/ja00461a011.
7. Cotton, F. A. (1967). "Structure and Bonding in Metal Carbonyls and Related Compounds". Helvetica Chimica Acta. 50: 117–130. doi:10.1002/hlca.19670500910.
8. Bau, Robert; Drabnis, Mary H. (1997). "Structures of Transition metal hydrides determined by neutron diffraction". Inorganica Chimica Acta. 259 (1–2): 27–50. doi:10.1016/S0020-1693(97)89125-6.
9. Schilter, David; Camara, James M.; Huynh, Mioy T.; Hammes-Schiffer, Sharon; Rauchfuss, Thomas B. (2016). "Hydrogenase Enzymes and Their Synthetic Models: The Role of Metal Hydrides". Chemical Reviews. 116 (15): 8693–8749. doi:10.1021/acs.chemrev.6b00180. PMC 5026416.

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