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The Chemistry of the
Transactinide Elements
Matthew MacLennan
CHEM 540C
1
Rf Db Sg Bh Hs Mt Ds Rg
2
Nuclear Effects
• Protons,
neutronsmagic
numbers
• 2, 8, 20, 28, 50, 82
• Island of stability
• Magic numbers are
not per...
Electronic Effects
• Relativistic effects –
orbital
contraction/expansion
• Spin-orbit coupling
Schädel, M. Angew. Chem. I...
Architecture of Periodic Table
Ds Rg
5
Preamble – “As Big as a Barn”
• Low production rates
• Barn = 10-24
cm2
; shed = 10-24
b
Schädel, M. J. Nucl. Radiochem. S...
Preamble Continued
• Need harsh conditions (acids)
• Detectable decay (i.e. not SF); usually α
7
Group 4
4
261
Rf78 s
8
Group 4
• MX4, MX6
2-
, MX7
3-
• Liquid-phase experiments confirm
Haba, H. et al. J. Am. Chem. Soc. 2004, 126, 5219-5224. 9
Group 4
• Test with pseudo-homologue Th, Pu
• 8M HNO3
• Chloride complexation Rf>Zr>Hf
Haba, H. et al. J. Nucl. Radiochem....
Group 5
5
?
262
Db34 s
11
Group 5
• Adsorption onto glass surfaces (KCl,
HNO3) (Group 4 = no sorption)
Hoffman, D.C.; Lee, D.M. J. Chem. Educ. 1999,...
Group 5
• Liquid-liquid extractions of Db, Ta, Nb, Pa in
TiOA, HCl/0.03 M HF
• Ta in organic phase
• Db eluting
between Nb...
Group 6
VI
?
?
X
255,256
Sg7-20 s
14
Group 6
• Group 6 forms neutral or anionic
oxides, oxyhalides
• HNO3/HF[MO3F]-
, [MO2F3]-
, MO2F2
• Pseudo-homologue U U...
Group 6
• Volatility MoO2Cl2>WO2Cl2≈SgO2Cl2
• Sg may be least volatile element yet
Türler, A. et al. Angew. Chem. Int. Ed...
Group 7
VII
?
?
X
X
267
Bh17 s
17
Group 7
• DFT calculationsMO3Cl most stable
• Volatility: TcO3Cl>ReO3Cl>BhO3Cl
Eichler, R. et al. Nature, 2000, 407, 63-6...
Group 8
VIII
?
?
X
X
269
Hs10 s
19
Group 8
Düllmann, Ch.E. et al. Czech. J. Phys., 2003, 53, A291-A298.
• Volatile tetroxides
• 2NaOH+HsO4Na2[HsO4(OH)2]
20
Group 9, 10, 11
IX X XI
?
?
X
X
Half-lives0.1 s
21
Group 12
XII
?
?
X
X
? ? ?
283
1123.8 s
22
Group 12
Eichler, R. et al. Nature, 2007, 447, 72-75.
• Covalent bond with Au
• Relativistic effects?
Eichler, R. et al. A...
“It’s Just a Phase You’re Going
Through…”
• 112 is more volatile than Hg!
• Gaseous metal?
Eichler, R. et al. Angew. Chem....
MX4 MO2X2
MOX4
MO3X MO4MX5
Some More Trends
?
?
X
X
? ? ? ?
25
Concluding Remarks
• Periodic table generally good tool
• Lacking for subtle properties
• Innovative experimental set-ups
...
Thank you so much!
27
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The Chemistry of the Transactinide Elements

  1. 1. The Chemistry of the Transactinide Elements Matthew MacLennan CHEM 540C 1
  2. 2. Rf Db Sg Bh Hs Mt Ds Rg 2
  3. 3. Nuclear Effects • Protons, neutronsmagic numbers • 2, 8, 20, 28, 50, 82 • Island of stability • Magic numbers are not permanent! • Spin-orbit coupling of neutrons and protons Warner, D. Nature 2004, 430, 517-519. Schiffer, J.P.; Freeman, S.J.; Caggiano, J.A.; Deibel, C.; Heinz, A.; Jiang, C.-L.; Lewis, R.; Parikh, A.; Parker, P.D.; Rehm, K.E.; Sinha, S.; Thomas, J.S. Phys. Rev. Lett. 2004, 92(16), 162501-1. 3
  4. 4. Electronic Effects • Relativistic effects – orbital contraction/expansion • Spin-orbit coupling Schädel, M. Angew. Chem. Int. Ed. 2006, 45, 368-401. 4
  5. 5. Architecture of Periodic Table Ds Rg 5
  6. 6. Preamble – “As Big as a Barn” • Low production rates • Barn = 10-24 cm2 ; shed = 10-24 b Schädel, M. J. Nucl. Radiochem. Sci. 2002, 3(1), 113-120. 6
  7. 7. Preamble Continued • Need harsh conditions (acids) • Detectable decay (i.e. not SF); usually α 7
  8. 8. Group 4 4 261 Rf78 s 8
  9. 9. Group 4 • MX4, MX6 2- , MX7 3- • Liquid-phase experiments confirm Haba, H. et al. J. Am. Chem. Soc. 2004, 126, 5219-5224. 9
  10. 10. Group 4 • Test with pseudo-homologue Th, Pu • 8M HNO3 • Chloride complexation Rf>Zr>Hf Haba, H. et al. J. Nucl. Radiochem. Sci. 2002, 3(1), 143-146. 10
  11. 11. Group 5 5 ? 262 Db34 s 11
  12. 12. Group 5 • Adsorption onto glass surfaces (KCl, HNO3) (Group 4 = no sorption) Hoffman, D.C.; Lee, D.M. J. Chem. Educ. 1999, 76(3), 331-347. 12
  13. 13. Group 5 • Liquid-liquid extractions of Db, Ta, Nb, Pa in TiOA, HCl/0.03 M HF • Ta in organic phase • Db eluting between Nb, Pa Schädel, M.; Angew. Chem. Intl. Ed. 2006, 45, 368-401. 13
  14. 14. Group 6 VI ? ? X 255,256 Sg7-20 s 14
  15. 15. Group 6 • Group 6 forms neutral or anionic oxides, oxyhalides • HNO3/HF[MO3F]- , [MO2F3]- , MO2F2 • Pseudo-homologue U UO2 2+ Schädel, M.; J. Alloys Compd. 1998, 271-273, 312-315. 15
  16. 16. Group 6 • Volatility MoO2Cl2>WO2Cl2≈SgO2Cl2 • Sg may be least volatile element yet Türler, A. et al. Angew. Chem. Int. Ed. 1999, 38, 2212-2213. 16
  17. 17. Group 7 VII ? ? X X 267 Bh17 s 17
  18. 18. Group 7 • DFT calculationsMO3Cl most stable • Volatility: TcO3Cl>ReO3Cl>BhO3Cl Eichler, R. et al. Nature, 2000, 407, 63-65. 18
  19. 19. Group 8 VIII ? ? X X 269 Hs10 s 19
  20. 20. Group 8 Düllmann, Ch.E. et al. Czech. J. Phys., 2003, 53, A291-A298. • Volatile tetroxides • 2NaOH+HsO4Na2[HsO4(OH)2] 20
  21. 21. Group 9, 10, 11 IX X XI ? ? X X Half-lives0.1 s 21
  22. 22. Group 12 XII ? ? X X ? ? ? 283 1123.8 s 22
  23. 23. Group 12 Eichler, R. et al. Nature, 2007, 447, 72-75. • Covalent bond with Au • Relativistic effects? Eichler, R. et al. Angew. Chem. Int. Ed. 2008, 47, 3262-3266. 23
  24. 24. “It’s Just a Phase You’re Going Through…” • 112 is more volatile than Hg! • Gaseous metal? Eichler, R. et al. Angew. Chem. Int. Ed. 2008, 47, 3262-3266. 24
  25. 25. MX4 MO2X2 MOX4 MO3X MO4MX5 Some More Trends ? ? X X ? ? ? ? 25
  26. 26. Concluding Remarks • Periodic table generally good tool • Lacking for subtle properties • Innovative experimental set-ups • Qualitativemore experiments to perform • 109-114 Nuclear Chemist when asked to provide a straight answer… 26
  27. 27. Thank you so much! 27

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