Metal carbonyl hydride
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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
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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
[edit]| 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
[edit]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
[edit]- 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
[edit]- ^ J. F. Hartwig; Organotransition metal chemistry - from bonding to catalysis. University Science Books. 2009. 753, 757-578. ISBN 978-1-891-38953-5.
- ^ 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.
- ^ Kaesz, H. D.; Saillant, R. B. (1972). "Hydride complexes of the transition metals". Chemical Reviews. 72 (3): 231–281. doi:10.1021/cr60277a003.
- ^ Holleman, Arnold F.; Wiberg, Egon; Wiberg, Nils (1995). Lehrbuch der anorganischen Chemie (in German). Berlin. ISBN 978-3-11-012641-9. OCLC 237142268.
{{cite book}}: CS1 maint: location missing publisher (link) - ^ Ralph G. Pearson. "The Transition-Metal-Hydrogen Bond". Chemical Reviews. 85: 1985. doi:10.1021/cr00065a002.
- ^ a b 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.
- ^ Cotton, F. A. (1967). "Structure and Bonding in Metal Carbonyls and Related Compounds". Helvetica Chimica Acta. 50: 117–130. doi:10.1002/hlca.19670500910.
- ^ 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.
- ^ 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.
External links
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