Solid-state NMR spectroscopic study of coordination compounds of XeF 2 with metal cations and the crystal structure of [Ba(XeF 2)5][AsF6]2II

Michael Gerken; Paul Hazendonk; Adriana Iuga; Jared Nieboer; Melita Tramšek; Evgeny Goreshnik; Boris Žemva; Shaohui Zheng; Jochen Autschbach

doi:10.1021/ic700557m

Solid-state NMR spectroscopic study of coordination compounds of XeF ₂ with metal cations and the crystal structure of [Ba(XeF ₂)₅][AsF₆]₂^II

Michael Gerken
, Paul Hazendonk
, Adriana Iuga
, Jared Nieboer
, Melita Tramšek
, Evgeny Goreshnik
, Boris Žemva
, Shaohui Zheng
, Jochen Autschbach

Chemistry

University of Lethbridge
Jožef Stefan Institute
SUNY Buffalo

Research output: Contribution to journal › Article › peer-review

20 Scopus citations

Abstract

The coordination compounds [Mg(XeF₂)₂][AsF ₆]₂, [Mg(XeF₂)₄][AsF ₆]₂, [Ca(XeF₂)_2.5][AsF ₆]₂, [Ba(XeF₂)₃][AsF ₆]₂, and [Ba(XeF₂)₅][AsF ₆]₂ were characterized by solid-state ¹⁹F and ¹²⁹Xe magic-angle spinning NMR spectroscopy. The ¹⁹F and ¹²⁹Xe NMR data of [Mg(XeF₂)₂][AsF ₆]2> [Mg(XeF₂)₄][AsF₆] ₂, and [Ca(XeF₂)_2.5][AsF₆] ₂ were correlated with the previously determined crystal structures. The isotropic ¹⁹F chemical shifts and ¹ J( ¹²⁹Xe-¹⁹F) coupling constants were used to distinguish the terminal and bridging coordination modes of XeF₂. Chemical-shift and coupling-constant calculations for [Mg(XeF₂)₄][AsF ₆]₂ confirmed the assignment of terminal and bridging chemical-shift and coupling-constant ranges. The NMR spectroscopic data of [Ba(XeF₂)₃][AsF₆]₂ and [Ba(XeF ₂)₅][AsF₆]₂ indicate the absence of any terminal XeF₂ ligands, which was verified for [Ba(XeF ₂)₅][AsF₆]₂ by its X-ray crystal structure. The adduct [Ba(XeF₂)₅][AsF₆] ₂ crystallizes in the space group Fmmm, with a = 11.6604(14) Å, b = 13.658(2) Å, c = 13.7802(17) Å, V = 2194.5(5) Å³ at -73°C, Z = 4, and R = 0.0350 and contains two crystallographically independent bridging XeF₂ molecules and one nonligating XeF₂ molecule. The AsF₆^- anions in [Mg(XeF₂)₄][AsF₆]₂, [Ca(XeF ₂)_2.5][AsF₆]₂, [Ba(XeF ₂)₃][AsF₆]₂, and [Ba(XeF ₂)₅][AsF₆]₂ were shown to be fluxional with the fluorines-on-arsenic being equivalent on the NMR time scale, emulating perfectly octahedral anion symmetry.

Original language	English
Pages (from-to)	6069-6077
Number of pages	9
Journal	Inorganic Chemistry
Volume	46
Issue number	15
DOIs	https://doi.org/10.1021/ic700557m
State	Published - Jul 23 2007

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10.1021/ic700557m

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@article{8f75ac179d914c23ac7695732bdc0c85,

title = "Solid-state NMR spectroscopic study of coordination compounds of XeF 2 with metal cations and the crystal structure of [Ba(XeF 2)5][AsF6]2II",

abstract = "The coordination compounds [Mg(XeF2)2][AsF 6]2, [Mg(XeF2)4][AsF 6]2, [Ca(XeF2)2.5][AsF 6]2, [Ba(XeF2)3][AsF 6]2, and [Ba(XeF2)5][AsF 6]2 were characterized by solid-state 19F and 129Xe magic-angle spinning NMR spectroscopy. The 19F and 129Xe NMR data of [Mg(XeF2)2][AsF 6]2> [Mg(XeF2)4][AsF6] 2, and [Ca(XeF2)2.5][AsF6] 2 were correlated with the previously determined crystal structures. The isotropic 19F chemical shifts and 1 J( 129Xe-19F) coupling constants were used to distinguish the terminal and bridging coordination modes of XeF2. Chemical-shift and coupling-constant calculations for [Mg(XeF2)4][AsF 6]2 confirmed the assignment of terminal and bridging chemical-shift and coupling-constant ranges. The NMR spectroscopic data of [Ba(XeF2)3][AsF6]2 and [Ba(XeF 2)5][AsF6]2 indicate the absence of any terminal XeF2 ligands, which was verified for [Ba(XeF 2)5][AsF6]2 by its X-ray crystal structure. The adduct [Ba(XeF2)5][AsF6] 2 crystallizes in the space group Fmmm, with a = 11.6604(14) {\AA}, b = 13.658(2) {\AA}, c = 13.7802(17) {\AA}, V = 2194.5(5) {\AA}3 at -73°C, Z = 4, and R = 0.0350 and contains two crystallographically independent bridging XeF2 molecules and one nonligating XeF2 molecule. The AsF6- anions in [Mg(XeF2)4][AsF6]2, [Ca(XeF 2)2.5][AsF6]2, [Ba(XeF 2)3][AsF6]2, and [Ba(XeF 2)5][AsF6]2 were shown to be fluxional with the fluorines-on-arsenic being equivalent on the NMR time scale, emulating perfectly octahedral anion symmetry.",

author = "Michael Gerken and Paul Hazendonk and Adriana Iuga and Jared Nieboer and Melita Tram{\v s}ek and Evgeny Goreshnik and Boris {\v Z}emva and Shaohui Zheng and Jochen Autschbach",

year = "2007",

month = jul,

day = "23",

doi = "10.1021/ic700557m",

language = "English",

volume = "46",

pages = "6069--6077",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "15",

}

TY - JOUR

T1 - Solid-state NMR spectroscopic study of coordination compounds of XeF 2 with metal cations and the crystal structure of [Ba(XeF 2)5][AsF6]2II

AU - Gerken, Michael

AU - Hazendonk, Paul

AU - Iuga, Adriana

AU - Nieboer, Jared

AU - Tramšek, Melita

AU - Goreshnik, Evgeny

AU - Žemva, Boris

AU - Zheng, Shaohui

AU - Autschbach, Jochen

PY - 2007/7/23

Y1 - 2007/7/23

N2 - The coordination compounds [Mg(XeF2)2][AsF 6]2, [Mg(XeF2)4][AsF 6]2, [Ca(XeF2)2.5][AsF 6]2, [Ba(XeF2)3][AsF 6]2, and [Ba(XeF2)5][AsF 6]2 were characterized by solid-state 19F and 129Xe magic-angle spinning NMR spectroscopy. The 19F and 129Xe NMR data of [Mg(XeF2)2][AsF 6]2> [Mg(XeF2)4][AsF6] 2, and [Ca(XeF2)2.5][AsF6] 2 were correlated with the previously determined crystal structures. The isotropic 19F chemical shifts and 1 J( 129Xe-19F) coupling constants were used to distinguish the terminal and bridging coordination modes of XeF2. Chemical-shift and coupling-constant calculations for [Mg(XeF2)4][AsF 6]2 confirmed the assignment of terminal and bridging chemical-shift and coupling-constant ranges. The NMR spectroscopic data of [Ba(XeF2)3][AsF6]2 and [Ba(XeF 2)5][AsF6]2 indicate the absence of any terminal XeF2 ligands, which was verified for [Ba(XeF 2)5][AsF6]2 by its X-ray crystal structure. The adduct [Ba(XeF2)5][AsF6] 2 crystallizes in the space group Fmmm, with a = 11.6604(14) Å, b = 13.658(2) Å, c = 13.7802(17) Å, V = 2194.5(5) Å3 at -73°C, Z = 4, and R = 0.0350 and contains two crystallographically independent bridging XeF2 molecules and one nonligating XeF2 molecule. The AsF6- anions in [Mg(XeF2)4][AsF6]2, [Ca(XeF 2)2.5][AsF6]2, [Ba(XeF 2)3][AsF6]2, and [Ba(XeF 2)5][AsF6]2 were shown to be fluxional with the fluorines-on-arsenic being equivalent on the NMR time scale, emulating perfectly octahedral anion symmetry.

AB - The coordination compounds [Mg(XeF2)2][AsF 6]2, [Mg(XeF2)4][AsF 6]2, [Ca(XeF2)2.5][AsF 6]2, [Ba(XeF2)3][AsF 6]2, and [Ba(XeF2)5][AsF 6]2 were characterized by solid-state 19F and 129Xe magic-angle spinning NMR spectroscopy. The 19F and 129Xe NMR data of [Mg(XeF2)2][AsF 6]2> [Mg(XeF2)4][AsF6] 2, and [Ca(XeF2)2.5][AsF6] 2 were correlated with the previously determined crystal structures. The isotropic 19F chemical shifts and 1 J( 129Xe-19F) coupling constants were used to distinguish the terminal and bridging coordination modes of XeF2. Chemical-shift and coupling-constant calculations for [Mg(XeF2)4][AsF 6]2 confirmed the assignment of terminal and bridging chemical-shift and coupling-constant ranges. The NMR spectroscopic data of [Ba(XeF2)3][AsF6]2 and [Ba(XeF 2)5][AsF6]2 indicate the absence of any terminal XeF2 ligands, which was verified for [Ba(XeF 2)5][AsF6]2 by its X-ray crystal structure. The adduct [Ba(XeF2)5][AsF6] 2 crystallizes in the space group Fmmm, with a = 11.6604(14) Å, b = 13.658(2) Å, c = 13.7802(17) Å, V = 2194.5(5) Å3 at -73°C, Z = 4, and R = 0.0350 and contains two crystallographically independent bridging XeF2 molecules and one nonligating XeF2 molecule. The AsF6- anions in [Mg(XeF2)4][AsF6]2, [Ca(XeF 2)2.5][AsF6]2, [Ba(XeF 2)3][AsF6]2, and [Ba(XeF 2)5][AsF6]2 were shown to be fluxional with the fluorines-on-arsenic being equivalent on the NMR time scale, emulating perfectly octahedral anion symmetry.

UR - https://www.scopus.com/pages/publications/34547673602

U2 - 10.1021/ic700557m

DO - 10.1021/ic700557m

M3 - Article

AN - SCOPUS:34547673602

SN - 0020-1669

VL - 46

SP - 6069

EP - 6077

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 15

ER -

Solid-state NMR spectroscopic study of coordination compounds of XeF ₂ with metal cations and the crystal structure of [Ba(XeF ₂)₅][AsF₆]₂^II

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