Plumbane (original) (raw)

From Wikipedia, the free encyclopedia

Plumbane

Skeletal formula of plumbaneSkeletal formula of plumbane
Spacefill model of plumbaneSpacefill model of plumbane Lead, Pb Hydrogen, H
Names
IUPAC name Plumbane
Other nameslead tetrahydride, tetrahydridolead, lead(IV) hydride, hydrogen plumbide
Identifiers
CAS Number 15875-18-0 ☒N
3D model (JSmol) Interactive image
ChEBI CHEBI:30181 checkY
ChemSpider 109888 checkY
PubChem CID 123278
CompTox Dashboard (EPA) DTXSID201319327 Edit this at Wikidata
InChI InChI=1S/Pb.4H checkYKey: XRCKXJLUPOKIPF-UHFFFAOYSA-N checkYInChI=1/Pb.4H/rH4Pb/h1H4Key: XRCKXJLUPOKIPF-BJORFFIVAF
SMILES [Pb]
Properties
Chemical formula PbH4
Molar mass 211.23 g/mol
Appearance Colorless gas
Boiling point −13 °C (9 °F; 260 K)
Structure
Molecular shape Tetrahedral at the Pb atom
Related compounds
Related tetrahydride compounds MethaneSilaneGermaneStannane
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). ☒N verify (what is checkY☒N ?) Infobox references

Chemical compound

Plumbane is an inorganic chemical compound with the chemical formula PbH4. It is a colorless gas. It is a metal hydride and group 14 hydride composed of lead and hydrogen.[1] Plumbane is not well characterized or well known, and it is thermodynamically unstable with respect to the loss of a hydrogen atom.[2] Derivatives of plumbane include lead tetrachloride, PbCl4, and tetraethyllead, (CH3CH2)4Pb.

Until recently, it was uncertain whether plumbane had ever actually been synthesized,[3] although the first reports date back to the 1920s[4] and in 1963, Saalfeld and Svec reported the observation of PbH+
4 by mass spectrometry.[5] Plumbane has repeatedly been the subject of Dirac–Hartree–Fock relativistic calculation studies, which investigate the stabilities, geometries, and relative energies of hydrides of the formula MH4 or MH2.[2][6][7]

Plumbane is an unstable colorless gas and is the heaviest group IV hydride;[8] and has a tetrahedral (Td) structure with an equilibrium distance between lead and hydrogen of 1.73 Å.[9] By weight, plumbane is 1.91% hydrogen and 98.09% lead. In plumbane, the formal oxidation states of hydrogen and lead are +1 and −4, respectively, because the electronegativity of lead(IV) is higher than that of hydrogen. The stability of hydrides MH4 (M = C–Pb) decreases as the atomic number of M increases.

Early studies of PbH4 revealed that the molecule is unstable as compared to its lighter congeners silane, germane, and stannane.[10] It cannot be made by methods used to synthesize GeH4 or SnH4.

In 1999, plumbane was synthesized from lead(II) nitrate, Pb(NO3)2, and sodium borohydride, NaBH4.[11] A non-nascent mechanism for plumbane synthesis was reported in 2005.[12]

In 2003, Wang and Andrews carefully studied the preparation of PbH4 by laser ablation and additionally identified the infrared (IR) bands.[13]

Congeners of plumbane include:

  1. ^ Porritt, C. J. (1975). Chem. Ind-London. 9: 398.
  2. ^ a b Hein, Thomas A.; Thiel, Walter; Lee, Timothy J. (1993). "Ab initio study of the stability and vibrational spectra of plumbane, methylplumbane, and homologous compounds". The Journal of Physical Chemistry. 97 (17): 4381–4385. doi:10.1021/j100119a021. hdl:11858/00-001M-0000-0028-1862-2.
  3. ^ Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochman, M. Advanced Inorganic Chemistry. Wiley: New York, 1999
  4. ^ Paneth, Fritz; Nörring, Otto (1920). "Über Bleiwasserstoff". Berichte der Deutschen Chemischen Gesellschaft (A and B Series). 53 (9): 1693–1710. doi:10.1002/cber.19200530915.
  5. ^ Saalfeld, Fred E.; Svec, Harry J. (1963). "The Mass Spectra of Volatile Hydrides. I. The Monoelemental Hydrides of the Group IVB and VB Elements". Inorganic Chemistry. 2: 46–50. doi:10.1021/ic50005a014.
  6. ^ Desclaux, J. P.; Pyykko, P. (1974). "Relativistic and non-relativistic Hartree-Fock one-centre expansion calculations for the series CH4 to PbH4 within the spherical approximation". Chemical Physics Letters. 29 (4): 534–539. Bibcode:1974CPL....29..534D. doi:10.1016/0009-2614(74)85085-2.
  7. ^ Pyykkö, P.; Desclaux, J. P. (1977). "Dirac–Fock one-centre calculations show (114)H4 to resemble PbH4". Nature. 266 (5600): 336–337. Bibcode:1977Natur.266..336P. doi:10.1038/266336a0. S2CID 4183019.
  8. ^ CRC Handbook of Chemistry and Physics Online Edition.
  9. ^ Visser, O.; Visscher, L.; Aerts, P. J. C.; Nieuwpoort, W. C. (1992). "Relativistic all-electron molecular Hartree-Fock-Dirac-(Breit) calculations on CH4, SiH4, GeH4, SnH4, PbH4". Theoretica Chimica Acta. 81 (6): 405–416. doi:10.1007/BF01134864. S2CID 97874625.
  10. ^ Malli, Gulzari L.; Siegert, Martin; Turner, David P. (2004). "Relativistic and electron correlation effects for molecules of heavy elements: Ab initio fully relativistic coupled-cluster calculations for PbH4". International Journal of Quantum Chemistry. 99 (6): 940–949. doi:10.1002/qua.20142.
  11. ^ Krivtsun, V. M.; Kuritsyn, Y. A.; Snegirev, E. P. (1999). "Observation of IR absorption spectra of the unstable PbH4 molecule" (PDF). Opt. Spectrosc. 86 (5): 686–691. Bibcode:1999OptSp..86..686K. Archived from the original (PDF) on 2016-03-04. Retrieved 2012-12-31.
  12. ^ Zou, Y; Jin, FX; Chen, ZJ; Qiu, DR; Yang, PY (2005). "Non-nascent hydrogen mechanism of plumbane generation". Guang Pu Xue Yu Guang Pu Fen Xi = Guang Pu. 25 (10): 1720–3. PMID 16395924.
  13. ^ Wang, Xuefeng; Andrews, Lester (2003). "Infrared Spectra of Group 14 Hydrides in Solid Hydrogen: Experimental Observation of PbH4, Pb2H2, and Pb2H4". Journal of the American Chemical Society. 125 (21): 6581–6587. doi:10.1021/ja029862l. PMID 12785799.