The Chemistry of the Transactinide Elements

Matthew MacLennanCHEM 540C

1

Rf Db Sg Bh Hs Mt Ds Rg

2

Nuclear Effects

• Protons, neutronsmagic 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

Electronic Effects

• Relativistic effects –orbital contraction/expansion

• Spin-orbit coupling

Schädel, M. Angew. Chem. Int. Ed. 2006, 45, 368-401. 4

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. Sci. 2002, 3(1), 113-120. 6

Preamble Continued

• Need harsh conditions (acids)• Detectable decay (i.e. not SF); usually α

7

Group 4

4

261Rf78 s

8

Group 4

• MX4, MX62-, 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. Sci. 2002, 3(1), 143-146. 10

Group 5

5?

262Db34 s

11

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

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

Group 6

VI? ?

X255,256Sg7-20 s

14

Group 6

• Group 6 forms neutral or anionic oxides, oxyhalides

• HNO3/HF[MO3F]-, [MO2F3]-, MO2F2

• Pseudo-homologue U UO22+

Schädel, M.; J. Alloys Compd. 1998, 271-273, 312-315. 15

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

Group 7

VII? ?

X

X

267Bh17 s

17

Group 7

• DFT calculationsMO3Cl most stable

• Volatility: TcO3Cl>ReO3Cl>BhO3Cl

Eichler, R. et al. Nature, 2000, 407, 63-65. 18

Group 8

VIII? ?

X

X

269Hs10 s

19

Group 8

Düllmann, Ch.E. et al. Czech. J. Phys., 2003, 53, A291-A298.

• Volatile tetroxides• 2NaOH+HsO4Na2[HsO4(OH)2]

20

Group 9, 10, 11

IX X XI? ?

X

XHalf-lives0.1 s

21

Group 12

XII? ?

X

X

? ? ?

2831123.8 s

22

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

“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

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• Qualitativemore experiments to perform• 109-114

Nuclear Chemist when askedto provide a straight answer…

26

Thank you so much!

27