Xenon hexafluoroplatinate: Difference between revisions
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==Structure== | ==Structure== | ||
The material described originally as "xenon hexafluoroplatinate" is probably not Xe<sup>+</sup>[PtF<sub>6</sub>]<sup>−</sup>. The main problem with this formulation is "Xe<sup>+</sup>", which would be a [[Radical (chemistry)|radical]] and would [[Dimer (chemistry)|dimerize]] or abstract a [[fluorine]] atom to give XeF<sup>+</sup>. Thus, Bartlett discovered that [[Xenon|Xe]] undergoes chemical reactions, but the nature and purity of his initial mustard yellow product remains uncertain.<ref name="grahm">{{cite journal |last1=Graham |first1=Lionell |last2=Graudejus |first2=Oliver |last3=Jha |first3=Narendra K. |last4=Bartlett |first4=Neil |author-link4=Neil Bartlett (chemist) |year=2000 |title=Concerning the nature of XePtF<sub>6</sub> |journal=[[Coordination Chemistry Reviews]] |volume=197 |issue=1 |pages=321–334 |doi=10.1016/S0010-8545(99)00190-3}}</ref> Further work indicates that Bartlett's product probably contained | The material described originally as "xenon hexafluoroplatinate" is probably not Xe<sup>+</sup>[PtF<sub>6</sub>]<sup>−</sup>. The main problem with this formulation is "Xe<sup>+</sup>", which would be a [[Radical (chemistry)|radical]] and would [[Dimer (chemistry)|dimerize]] or abstract a [[fluorine]] atom to give XeF<sup>+</sup>. Thus, Bartlett discovered that [[Xenon|Xe]] undergoes chemical reactions, but the nature and purity of his initial mustard yellow product remains uncertain.<ref name="grahm">{{cite journal |last1=Graham |first1=Lionell |last2=Graudejus |first2=Oliver |last3=Jha |first3=Narendra K. |last4=Bartlett |first4=Neil |author-link4=Neil Bartlett (chemist) |year=2000 |title=Concerning the nature of XePtF<sub>6</sub> |journal=[[Coordination Chemistry Reviews]] |volume=197 |issue=1 |pages=321–334 |doi=10.1016/S0010-8545(99)00190-3}}</ref> Further work indicates that Bartlett's product probably also contained products of further oxidation by PtF<sub>6</sub>, platinum(V) derivatives PtF<sub>5</sub>, [XeF]<sup>+</sup>[PtF<sub>5</sub>]<sup>−</sup>, and [XeF]<sup>+</sup>[Pt<sub>2</sub>F<sub>11</sub>]<sup>−</sup>.<ref name="grahm" /><ref name=Holleman>{{cite book |last1=Holleman |first1=Arnold Frederick |last2=Wiberg |first2=Egon |year=2001 |title=Inorganic Chemistry |publisher=[[Academic Press]] |location=San Diego |isbn=0-12-352651-5}}</ref> The title "compound" is a salt, consisting of an [[octahedral]] [[anionic]] [[fluoride]] complex of [[platinum]] and various xenon cations.<ref>{{cite book |last=Sampson |first=Mark T. |date=May 23, 2006 |title=Neil Bartlett and the Reactive Noble Gases |series=[[National Historic Chemical Landmarks]] |publisher=[[American Chemical Society]] |url=https://www.acs.org/content/dam/acsorg/education/whatischemistry/landmarks/bartlettnoblegases/neil-bartlett-reactive-noble-gases-commemorative-booklet.pdf |access-date=June 12, 2017 |url-status=live |archive-date=April 18, 2016 |archive-url=https://web.archive.org/web/20160418173907/https://www.acs.org/content/dam/acsorg/education/whatischemistry/landmarks/bartlettnoblegases/neil-bartlett-reactive-noble-gases-commemorative-booklet.pdf}}</ref> | ||
It has been proposed that the platinum fluoride forms a negatively charged [[polymer]]ic | It has been proposed that the platinum fluoride forms a negatively charged [[polymer]]ic anion with xenon fluoride [[cation]]s. A preparation of "XePtF<sub>6</sub>" by reaction of [[Xenon difluoride|XeF<sub>2</sub>]] and [[Platinum tetrafluoride|PtF<sub>4</sub>]] in anhydrous [[hydrogen fluoride|HF]] solution results in a solid which has been characterized as a {{chem|[PtF|5|]|-}} polymeric or [[Oligomer|oligomeric]] anion associated with XeF<sup>+</sup>. Such F-bridged polymeric chains and tetrameric ring with pendant XeF<sup>+</sup> units have been observed in the crystal structures of the analogous compounds XeCrF<sub>6</sub> (XeF<sub>2</sub>∙CrF<sub>4</sub>)<ref>{{Cite journal |last=Lutar |first=K. |last2=Leban |first2=I. |last3=Ogrin |first3=T. |last4=Žemva |first4=B. |title=XeF2·CrF4 and (XeF5+CrF5–)4·XeF4: Syntheses, Crystal Structures and Some Properties |journal=European Journal of Solid State and Inorganic Chemistry |volume=29 |issue=4–5 |pages=713–727}}</ref> and XeMnF<sub>6</sub> (XeF<sub>2</sub>∙MnF<sub>4</sub>),<ref>{{Cite journal |last=Motaln |first=Klemen |last2=Gurung |first2=Kshitij |last3=Brázda |first3=Petr |last4=Kokalj |first4=Anton |last5=Radan |first5=Kristian |last6=Dragomir |first6=Mirela |last7=Žemva |first7=Boris |last8=Palatinus |first8=Lukáš |last9=Lozinšek |first9=Matic |date=2024-09-25 |title=Reactive Noble-Gas Compounds Explored by 3D Electron Diffraction: XeF2–MnF4 Adducts and a Facile Sample Handling Procedure |url=https://doi.org/10.1021/acscentsci.4c00815 |journal=ACS Central Science |volume=10 |issue=9 |pages=1733–1741 |doi=10.1021/acscentsci.4c00815 |issn=2374-7943 |pmc=11428288 |pmid=39345812}}</ref> respectively. These structures could serve as structural models for XePtF<sub>6</sub>. | ||
==History== | ==History== | ||
{{Main|Noble gas compound}} | {{Main|Noble gas compound}} | ||
In 1962, [[Neil Bartlett (chemist)|Neil Bartlett]] discovered that a mixture of platinum hexafluoride gas and oxygen formed a red solid.<ref name="bartlett">{{cite journal |last=Bartlett |first=Neil |author-link=Neil Bartlett (chemist) |year=1962 |title=Xenon hexafluoroplatinate(V) Xe<sup>+</sup>[PtF<sub>6</sub>]<sup>−</sup> |journal=[[Proceedings of the Chemical Society]] |doi=10.1039/PS9620000197 |volume=1962 |issue=6 |pages=197–236}}</ref><ref>{{cite journal |last1=Bartlett |first1=Neil |author-link1=Neil Bartlett (chemist) |last2=Lohmann |first2=D. H. |year=1962 |title=Dioxygenyl hexafluoroplatinate(V), {{chem|O|2|+}}[PtF<sub>6</sub>]<sup>−</sup> |journal=[[Proceedings of the Chemical Society]] |doi=10.1039/PS9620000097 |volume=1962 |issue=3 |pages=97–132}}</ref> The red solid turned out to be [[dioxygenyl hexafluoroplatinate]], {{nowrap|{{chem|O|2|+}}[PtF<sub>6</sub>]<sup>−</sup>.}} Bartlett noticed that the ionization energy for O<sub>2</sub> (1175 kJ mol<sup>−1</sup>) was very close to the ionization energy for Xe (1170 kJ mol<sup>−1</sup>). He then asked his colleagues to give him some xenon "so that he could try out some reactions",<ref>{{cite book |last1=Clugston |first1=Michael |last2=Flemming |first2=Rosalind |year=2000 |title=Advanced Chemistry |publisher=[[Oxford University Press]] |isbn=978-0199146338 |page=355}}</ref> whereupon he established that xenon indeed reacts with PtF<sub>6</sub>. Although, as discussed above, the product was probably a mixture of several compounds, Bartlett's work was the first proof that compounds could be prepared from a [[noble gas]]. Since Bartlett's observation, many well-defined [[Xenon compounds|compounds of xenon]] have been reported including [[Xenon difluoride|XeF<sub>2</sub>]], [[Xenon tetrafluoride|XeF<sub>4</sub>]], and [[Xenon hexafluoride|XeF<sub>6</sub>]].<ref name = Holleman /> | In 1962, [[Neil Bartlett (chemist)|Neil Bartlett]] discovered that a mixture of platinum hexafluoride gas and oxygen formed a red solid.<ref name="bartlett">{{cite journal |last=Bartlett |first=Neil |author-link=Neil Bartlett (chemist) |year=1962 |title=Xenon hexafluoroplatinate(V) Xe<sup>+</sup>[PtF<sub>6</sub>]<sup>−</sup> |journal=[[Proceedings of the Chemical Society]] |doi=10.1039/PS9620000197 |volume=1962 |issue=6 |pages=197–236}}</ref><ref>{{cite journal |last1=Bartlett |first1=Neil |author-link1=Neil Bartlett (chemist) |last2=Lohmann |first2=D. H. |year=1962 |title=Dioxygenyl hexafluoroplatinate(V), {{chem|O|2|+}}[PtF<sub>6</sub>]<sup>−</sup> |journal=[[Proceedings of the Chemical Society]] |doi=10.1039/PS9620000097 |volume=1962 |issue=3 |pages=97–132}}</ref> The red solid turned out to be [[dioxygenyl hexafluoroplatinate]], {{nowrap|{{chem|O|2|+}}[PtF<sub>6</sub>]<sup>−</sup>.}} Bartlett noticed that the ionization energy for O<sub>2</sub> (1175 kJ mol<sup>−1</sup>) was very close to the ionization energy for Xe (1170 kJ mol<sup>−1</sup>). He then asked his colleagues to give him some xenon "so that he could try out some reactions",<ref>{{cite book |last1=Clugston |first1=Michael |last2=Flemming |first2=Rosalind |year=2000 |title=Advanced Chemistry |publisher=[[Oxford University Press]] |isbn=978-0199146338 |page=355}}</ref><ref>{{Cite journal |last=Hargittai |first=István |date=2009 |title=Neil Bartlett and the first noble-gas compound |url=http://link.springer.com/10.1007/s11224-009-9526-9 |journal=Structural Chemistry |language=en |volume=20 |issue=6 |pages=953–959 |doi=10.1007/s11224-009-9526-9 |issn=1040-0400}}</ref> whereupon he established that xenon indeed reacts with PtF<sub>6</sub>. Although, as discussed above, the product was probably a mixture of several compounds, Bartlett's work was the first proof that compounds could be prepared from a [[noble gas]]. Since Bartlett's observation, many well-defined [[Xenon compounds|compounds of xenon]] have been reported including [[Xenon difluoride|XeF<sub>2</sub>]], [[Xenon tetrafluoride|XeF<sub>4</sub>]], and [[Xenon hexafluoride|XeF<sub>6</sub>]].<ref name = Holleman /> | ||
==See also== | ==See also== | ||
Latest revision as of 19:36, 3 June 2025
Xenon hexafluoroplatinate is the product of the reaction of platinum hexafluoride with xenon, in an experiment that proved the chemical reactivity of the noble gases. This experiment was performed by Neil Bartlett at the University of British Columbia, who formulated the product as "Xe+[PtF6]−", although subsequent work suggests that Bartlett's product was probably a salt mixture and did not in fact contain this specific salt.[1]
Preparation
"Xenon hexafluoroplatinate" is prepared from xenon and platinum hexafluoride (PtF6) as gaseous solutions in SF6. The reactants are combined at 77 K and slowly warmed to allow for a controlled reaction.
Structure
The material described originally as "xenon hexafluoroplatinate" is probably not Xe+[PtF6]−. The main problem with this formulation is "Xe+", which would be a radical and would dimerize or abstract a fluorine atom to give XeF+. Thus, Bartlett discovered that Xe undergoes chemical reactions, but the nature and purity of his initial mustard yellow product remains uncertain.[2] Further work indicates that Bartlett's product probably also contained products of further oxidation by PtF6, platinum(V) derivatives PtF5, [XeF]+[PtF5]−, and [XeF]+[Pt2F11]−.[2][3] The title "compound" is a salt, consisting of an octahedral anionic fluoride complex of platinum and various xenon cations.[4]
It has been proposed that the platinum fluoride forms a negatively charged polymeric anion with xenon fluoride cations. A preparation of "XePtF6" by reaction of XeF2 and PtF4 in anhydrous HF solution results in a solid which has been characterized as a Template:Chem polymeric or oligomeric anion associated with XeF+. Such F-bridged polymeric chains and tetrameric ring with pendant XeF+ units have been observed in the crystal structures of the analogous compounds XeCrF6 (XeF2∙CrF4)[5] and XeMnF6 (XeF2∙MnF4),[6] respectively. These structures could serve as structural models for XePtF6.
History
Script error: No such module "Labelled list hatnote". In 1962, Neil Bartlett discovered that a mixture of platinum hexafluoride gas and oxygen formed a red solid.[7][8] The red solid turned out to be dioxygenyl hexafluoroplatinate, Template:Chem[PtF6]−. Bartlett noticed that the ionization energy for O2 (1175 kJ mol−1) was very close to the ionization energy for Xe (1170 kJ mol−1). He then asked his colleagues to give him some xenon "so that he could try out some reactions",[9][10] whereupon he established that xenon indeed reacts with PtF6. Although, as discussed above, the product was probably a mixture of several compounds, Bartlett's work was the first proof that compounds could be prepared from a noble gas. Since Bartlett's observation, many well-defined compounds of xenon have been reported including XeF2, XeF4, and XeF6.[3]
See also
References
Template:Xenon compounds Template:Noble gas compounds Template:Platinum compounds
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