Cadmium hydride

Nomenclature

The systematic name cadmium dihydride, a valid IUPAC name, is constructed according to the compositional nomenclature. Cadmium dihydride is also used to refer to the related molecular compound dihydridocadmium and its oligomers. Care should be taken to avoid confusing the two compounds.

Cadmium hydride is also used as a compositional IUPAC name for the compound with the chemical formula CdH.

History

In 1950 a research group led by Glenn D. Barbaras, synthesized cadmium hydride for the first time. This reaction sequence consisted of demethylation of dimethylcadmium in diethyl ether at −78 °C, to cadmium hydride.

Chemical properties

Solid cadmium hydride, on the basis of its infrared spectrum, is believed to contain hydrogen-bridge bonds. Other lower metal hydrides polymerize in a similar fashion. Unless cooled below −20 C, cadmium hydride rapidly decomposes to produce cadmium and hydrogen: : → n Cd + n

Dihydridocadmium

is the monomeric, molecular form with the chemical formula (also written ). It is a colorless gas that does not persist undiluted. has a low activation barrier toward autopolymerisation into the standard form of cadmium hydride and would rapidly do so in undiluted concentrations. Since the activation barrier for the reverse reaction is much greater than that of the decomposition reaction, autopolymerisation of may be considered as irreversible for most intents and purposes. It was produced by the gas phase reaction of excited cadmium atoms with dihydrogen, H2, and the structure determined high-resolution infrared emission spectra. The molecule is linear, with a bond length of 168.3 pm.

Chemical properties

The two-coordinate group (-CdH) in such as can accept an electron-pair donating ligand into the molecule by adduction: :] + L → Because of this acceptance of the electron-pair donating ligand (L), has Lewis-acidic character. can accept two electron-pairs from ligands, as in the case of the tetrahydridocadmate(2−) anion ().

The compound, Cs3CdH5, prepared by the reaction of caesium hydride, CsH, and cadmium metal powder at high temperature contains the ion, along with caesium cations, Cs+, and hydride anions, H−. The tetrahedral anion is an example of an ionic complex of CdH2. The average Cd-H bond length in is 182pm.

In gaseous , the molecules form groups (trimers), being connected by van der Waals forces. The dissociation enthalpy of the dimer is estimated at 8.8 kJ mol−1.

References

References

1. {{PGCH. 0087
2. (October 1951). "The Preparation of the Hydrides of Zinc, Cadmium, Beryllium, Magnesium and Lithium by the Use of Lithium Aluminum Hydride". ACS Publications.
3. (December 2004). "Infrared Spectra of Zn and Cd Hydride Molecules and Solids". ACS Publications.
4. (2005). "Gaseous HgH₂, CdH₂, and ZnH₂". Chemistry: A European Journal.
5. (1999). "Synthesis and structure determination of the first ternary cadmium hydride, Cs₃CdH₅". Journal of Alloys and Compounds.