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Part II: Recent Progress in Xe(II) and Xe(IV)

Oxide Fluoride Chemistry

University of Oulu, Finland

Main-Group Chemistry Summer School

August 27-31, 2012

Lecture II

2 M. Gerken, B.E. Pointner, M. Moran, G.J. Schrobilgen, H.P.A. Mercier, J.A. Boatz, B. Hoge, K.O. Christe, J. Am. Chem. Soc., 2009, 131, 13474.

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8 M.D. Moran, D. Brock, H.P.A. Mercier, G.J. Schrobilgen, J. Am. Chem. Soc., 2010, 132, 13823.

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10 M.D. Moran, D. Brock, H.P.A. Mercier, G.J. Schrobilgen, J. Am. Chem. Soc., 2010, 132, 13823.

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Synthesis of FXeOClO2

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Synthesis of FXeOClO2

FXeOXeFXeF+ has been used to prepare FXeOClO2 in a reaction

analogous to that used to prepare FXeONO2. •

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NMR Spectra of FXeOClO2

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XeO2

Xenon(IV) Species

n = 0 or 1

XeF4 XeOF2 XeO2 FxXe(OTeF5)4-x O=XeFn(OTeF5)2-n *

XeOF2∙nHF

F2OXeN≡CCH3 F3XeOIOF4

XeF3+ XeOF+ C6F5XeF2

+ Xe(OTeF5)3+ *

HOXeF2+ *

HOXe(F)2OXeF2+ * FXeIIOXeIVF2

+ *

FXeIIOXeIV(F)2OXeIVF2+ *

XeF5¯ XeOF3

¯ XeO2F¯

Unknown. * Not fully characterized.

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17 D.S. Brock, V. Bilir, H.P.A. Mercier, G.J. Schrobilgen J. Am. Chem. Soc. 2007, 129, 3598.

18 D. Brock, H.P.A. Mercier, G.J. Schrobilgen, J. Am. Chem. Soc., 2010, 132, 10935.

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XeOF2·nHF + AsF5 HOXeF2+AsF6

– + (n-1)HF

HOXeF2+AsF6

– XeF+AsF6– + HF + ½O2

HF

1h @ –78 oC

–35 oC

rapid out-gassing

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26 26

XeO2 & Earth’s Missing Xenon

• Studies have shown that as much as 90% of the

Earth’s primordial xenon is absent from its

atmosphere.

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M. Ozima, F. A. Podosek, J. Geophys. Res. 1999, 104, 25493.

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• It has been proposed that xenon displaces silicon from

quartz (SiO2) at the high pressures (0.7−5 GPa) and

temperatures (500−1500 K) that are encountered in the

continental crust.

• A “(Si, Xe)O2 network” was proposed based on X-ray

powder diffraction and Raman spectroscopy

SiO2(quartz) + Xe(s) Si(s) + XeO2(s)

C. Sanloup, B. C. Schmidt, E. M. C. Perrez, A. Jambon, E. Gregoryanz, M. Mezouar,

Science 2005, 310, 1174-1177.

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Known Xenon Oxides

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[Na]4[XeO6] + 2H2SO4 XeO4 + 2[Na]2[SO4] + 2H2O

XeF6 + 3H2O XeO3 + 6HF

4XeF4 + 8H2O 2XeO3 + 2Xe + O2 + 16HF

• An early study reported the hydrolysis of XeF4 and the

formation of a transient yellow-colored solid in pure and

acidified (H2SO4) water at 0 oC. The yellow product was

never isolated or characterized.

H2SO4 (conc.)

D. F. Smith J. Am. Chem. Soc. 1963, 85, 816.

D. H. Templeton, A. Zalkin, J. D. Forrester, S. M. Williamson, J. Am. Chem. Soc. 1963, 85, 817.

H. Selig, H. H. Claassen, C. L. Chernick, J. G. Malm, J. L. Huston, Science 1964, 143, 1322-1323.

E. H. Appelman, J. G. Malm, J. Am. Chem. Soc. 1964, 86, 2141-2148.

S. M. Williamson, C. W. Koch In Noble Gas Compounds; H. H. Hyman, Ed.;

University of Chicago Press: Chicago, 1963, pp 149−151.

pale yellow solid

colorless solid

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• XeF4 was hydrolyzed in excess H2O and the resulting

suspension centrifuged at 0 oC, followed by quenching the

mixture at −78 oC.

XeF4 + 2H2O(excess) XeO2 + 4HF

• The product was characterized by low-temperature Raman

spectroscopy with the use of 1/2H- and 16/18O-isotopic

enrichment. The spectra were consistent with the formation

of XeO2.

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XeO2

0 oC

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XeF4 + 2H2O(excess) XeO2 + 4HF 0 oC

XeF4 crystals

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XeO2

31 Asterisks (*) denote lines arising from the FEP sample tube and † denotes a laser artifact.

18O

16O

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XeF4 Xe16O2 Xe16/18O2 Xe18O2

D2d assgnts (L = F, O)

586 n6, n(Eu) 632.3(1) 626.5sh 625.8(1) n(E) nas(XeLt − XeLt)

554 n1, n(A1g) 570.3(100) 550.9(100) 542.6(100) n(A1)

n(B2)

ns(XeL4)

524 n4, n(B2g) nas(XeL2t − XeL2t)

291 n3, n(A2u) 283.9(3) 276.9(2) 270.0(3) n(B2) d(XeL4) o.o.p., umbrella mode

218 n2, n(B1g) 239.1(2)

227.9(4)

231sh

221.3(4)

226.6(2)

216.9(6) n(B1) d(XeL2c + XeL2c)

n.o. n5, n(B2u) n.o. n.o. n.o. n(A2) d(XeL2t) o.o.p. – d(XeL2t) o.o.p.

161 n7, n(Eu) 168.9(13) 165.0(19) 161.1(13) n(E) d(XeL2t) i.p.

99.5(14) 99.3(17) 99.5(15) lattice mode

D.S. Brock, G.J. Schrobilgen, J. Am. Chem. Soc. 2011, 133, 6265–6269.

(D4h)