“Plumbane”的意思、由来-开放百科全书

Plumbane, PbH₄, 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 tetrafluoride, (PbF₄), and tetraethyllead, ((CH₃CH₂)₄Pb).

History

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 {{chem|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]

Properties

Plumbane is an unstable colorless gas and is the heaviest group IV hydride.^[8] Furthermore, plumbane has a tetrahedral (T_d) structure with an equilibrium distance between lead and hydrogen of 1.73 Å.^[9] By weight percent, the composition of 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 hydrogen is higher than that of lead. The stability of metal hydrides with the formula MH₄ (M = C–Pb) decreases as the atomic number of M increases.

Preparation

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

References

1. ^{{cite journal | last1 = Porritt | first1 = C. J. | year = 1975 | title = | url = | journal = Chem. Ind-London | volume = 9 | issue = | page = 398 }}
2. ^¹{{cite journal | doi = 10.1021/j100119a021 | pages= 4381–4385 | title = Ab initio study of the stability and vibrational spectra of plumbane, methylplumbane, and homologous compounds | year = 1993 | last1 = Hein | first1 = Thomas A. | last2 = Thiel | first2 = Walter | last3 = Lee | first3 = Timothy J. | journal = The Journal of Physical Chemistry | volume = 97 | issue = 17}}
3. ^Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochman, M. Advanced Inorganic Chemistry. Wiley: New York, 1999
4. ^{{cite journal | doi = 10.1002/cber.19200530915 | pages = 1693–1710 | title = Über Bleiwasserstoff | year = 1920 | last1 = Paneth | first1 = Fritz | last2 = Nörring | first2 = Otto | journal = Berichte der deutschen chemischen Gesellschaft (A and B Series) | volume = 53 | issue = 9}}
5. ^{{cite journal | doi = 10.1021/ic50005a014| pages= 46–50 | title = The Mass Spectra of Volatile Hydrides. I. The Monoelemental Hydrides of the Group IVB and VB Elements | year = 1963 | last1 = Saalfeld | first1 = Fred E. | last2 = Svec | first2 = Harry J. | journal = Inorganic Chemistry | volume = 2}}
6. ^{{cite journal | doi =10.1016/0009-2614(74)85085-2| pages= 534–539 | title =Relativistic and non-relativistic Hartree-Fock one-centre expansion calculations for the series CH₄ to PbH₄ within the spherical approximation | year =1974 | last1 =Desclaux | first1 =J. P. | last2 =Pyykko | first2 =P. | journal =Chemical Physics Letters | volume =29 | issue =4}}
7. ^{{cite journal | pages= 336–337 | doi =10.1038/266336a0 | title= Dirac–Fock one-centre calculations show (114)H₄ to resemble PbH₄ | year= 1977 | last1= Pyykkö | first1= P. | last2= Desclaux | first2= J. P. | journal= Nature | volume= 266 | issue= 5600}}
8. ^CRC Handbook of Chemistry and Physics Online Edition.
9. ^{{cite journal | doi =10.1007/BF01134864 | pages=405–416 | title =Relativistic all-electron molecular Hartree-Fock-Dirac-(Breit) calculations on CH₄, SiH₄, GeH₄, SnH₄, PbH₄ | year =1992 | last1 =Visser | first1 =O. | last2 =Visscher | first2 =L. | last3 =Aerts | first3 =P. J. C. | last4 =Nieuwpoort | first4 =W. C. | journal =Theoretica Chimica Acta | volume =81 | issue =6}}
10. ^{{cite journal | doi =10.1002/qua.20142 | pages=940–949 | title =Relativistic and electron correlation effects for molecules of heavy elements: Ab initio fully relativistic coupled-cluster calculations for PbH₄ | year =2004 | last1 =Malli | first1 =Gulzari L. | last2 =Siegert | first2 =Martin | last3 =Turner | first3 =David P. | journal =International Journal of Quantum Chemistry | volume =99 | issue =6}}
11. ^{{cite journal | last1 = Krivtsun | first1 = V. M. | last2 = Kuritsyn | first2 = Y. A. | last3 = Snegirev | first3 = E. P. | year = 1999 | title = Observation of IR absorption spectra of the unstable PbH₄ molecule | url = http://www.isan.troitsk.ru/dms/tdl/publ/1999os_en.pdf | format = PDF | journal = Opt. Spectrosc | volume = 86 | issue = | pages = 686–691 }}
12. ^{{cite journal | pmid =16395924 | year =2005 | last1 =Zou | first1 =Y | last2 =Jin | first2 =FX | last3 =Chen | first3 =ZJ | last4 =Qiu | first4 =DR | last5 =Yang | first5 =PY | title =Non-nascent hydrogen mechanism of plumbane generation | volume =25 | issue =10 | pages =1720–3 | journal =Guang pu xue yu guang pu fen xi = Guang pu}}
13. ^{{cite journal | doi =10.1021/ja029862l | pages=6581–6587 | title =Infrared Spectra of Group 14 Hydrides in Solid Hydrogen: Experimental Observation of PbH₄, Pb₂H₂, and Pb₂H₄ | year =2003 | last1 =Wang | first1 =Xuefeng | last2 =Andrews | first2 =Lester | journal =Journal of the American Chemical Society | volume =125 | issue =21 | pmid =12785799}}