Metal‐Xenon Complexes

Seppelt, Konrad

doi:10.1002/zaac.200300226

Cited by 47 publications

(24 citation statements)

References 35 publications

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“…Among metal hexafluoroantimonates coordinated with HF the compound [Hg(HF)](SbF 6 ) 2 should be mentioned [17] [18]. The distance Au-F(HF) is 213.5(3) pm [19] and is comparable with Au-F(Sb) distance of 212.6(3) pm.…”

Section: Synthesis and Structures Of Other Coordination Compounds Witmentioning

confidence: 97%

Synthesis of novel salts with HF, AsF3 and XeF2 as ligands to metal cations

Tramšek

Žemva

2006

Journal of Fluorine Chemistry

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Section: Synthesis and Structures Of Other Coordination Compounds Witmentioning

confidence: 97%

Synthesis of novel salts with HF, AsF3 and XeF2 as ligands to metal cations

Tramšek

Žemva

2006

Journal of Fluorine Chemistry

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“…+ , [5,6] [Ag(S 8 ) 2 ] + , [1] [Au(Xe) 4 ] + , [14] [AgA C H T U N G T R E N N U N G (P 3 N 3 Cl 6 ) n ] + , [3] [AgA C H T U N G T R E N N U N G (C 2 H 2 ) n ] + , [15] {[AgA C H T U N G T R E N N U N G {Cp*Fe(P 5 )} 2 ] + ) 1 , [4] or [AgA C H T U N G T R E N N U N G (C 2 H 4 ) n ]…”

Section: A C H T U N G T R E N N U N G (P 4 S 3 ) N ] + (N = 1-3) Andmentioning

confidence: 99%

Dynamics and Counterion‐Dependence of the Structures of Weakly Bound Ag⁺–P₄S₃ Complexes

Raabe¹,

Antonijevic²,

Krossing³

2007

Chemistry A European J

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In an earlier publication (J. Am. Chem. Soc. 2002, 124, 7111) we showed that polymeric cationic [Ag(P(4)S(3))(n)](+) complexes (n=1, 2) are accessible if partnered with a suitable weakly coordinating counterion of the type [Al(OR(F))(4)](-) (OR(F): poly- or perfluorinated alkoxide). The present work addresses the following questions that could not be answered in the initial report: How many P(4)S(3) cages can be bound to a Ag(+) ion? Why are these complexes completely dynamic in solution in the (31)P NMR experiments? Can these dynamics be frozen out in a low-temperature (31)P MAS NMR experiment? What are the principal binding sites of the P(4)S(3) cage towards the Ag(+) ion? What are likely other isomers on the [Ag(P(4)S(3))(n)](+) potential energy surface? Counterion influence: Reactions of P(4)S(3) with Ag[Al{OC(CH(3))(CF(3))(2)}(4)] (Ag[hftb]) and Ag[{(CF(3))(3)CO}(3)Al-F-Al{OC(CF(3))(3))}(3)] (Ag[al-f-al]) gave [(P(4)S(3))Ag[hftb]](infinity) (7) as a molecular species, whereas [Ag(2)(P(4)S(3))(6)](2+)[al-f-al](-) (2) (8) is an isolated 2:1 salt. We suggest that a maximum of three P(4)S(3) cages may be bound on average to an Ag(+) ion. Only isolated dimeric dications are formed with the largest cation, but polymeric species are obtained with all other smaller aluminates. Thermodynamic Born-Haber cycles, DFT calculations, as well as solution NMR and ESI mass spectrometry indicate that 8 exhibits an equilibrium between the dication [Ag(2)(P(4)S(3))(6)](2+) (in the solid state) and two [Ag(P(4)S(3))(3)](+) monocations (in the gas phase and in solution). Dynamics: (31)P MAS NMR spectroscopy showed these solid adducts to be highly dynamic, to an extent that the (2)J(P,P) coupling within the cages could be resolved (J-res experiment). This is supported by DFT calculations, which show that the extended PES of [Ag(P(4)S(3))(n)](+) (n=1-3) and [Ag(2)(P(4)S(3))(2)](+) is very flat. The structures of alpha- and gamma-P(4)S(3) were redetermined. Their variable-temperature (31)P MAS NMR spectra are discussed jointly with those of all four currently known [Ag(P(4)S(3))(n)](+) adducts with n=1, 2, and 3.

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“…Hence, Xe in complex 3 is shielded in the region of 719-1,044 ppm compared with an unbound Xe atom, and the known chemical-shift range for 129 Xe has been increased by Ϸ800 ppm (or nearly 10%) to Ϸ8,400 ppm (32). Smaller shifts to high field (up to 50 ppm) have been observed for gaseous Xe trapped in Cu ϩ -or Ag ϩ -exchanged NaX or NaY zeolites (35), for which it is postulated that the increased shielding is caused by back donation from the d 10 Cu or Ag centers that occurs in transient interactions with the Xe. Theoretical calculations on Cu ϩ -Xe and Ag ϩ -Xe species predict these upfield shifts and show their source to be a mixing of the filled metal d shell with the 5p, 4p, and 3p orbitals on the Xe (36).…”

Section: Nmr Studies At Low Temperature In Lxementioning

confidence: 99%

“…The great majority of this noble gas chemistry has resulted from interaction of Kr and Xe with electron-deficient, highly oxidizing reagents to create compounds containing the noble gas in positive oxidation states (6). More recently, the occurrence of atomic Xe as a discrete ligand in a selection of cationic gold and mercury inorganic complexes has been demonstrated, with the bonding occurring through a lone pair of electrons on the Xe (7)(8)(9)(10). Theoretical studies had previously predicted high stability of such cationic gold complexes (11).…”

mentioning

confidence: 99%