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Copper(I) and Silver(I) Bis(trifluoromethanesulfonyl)imide and Their Interaction with an Arene, Diverse Olefins, and an NTf 2 − ‐Based Ionic Liquid
The chemistry of coinage metal bis(triflyl)imides of technological interest, CuNTf 2 and AgNTf 2 , their synthesis and complexes with excess of comparatively weakly coordinating NTf 2 − as well as with ether, olefins, and the arene mesitylene are described. The existence of the solvent‐free pure pha...
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| Published in: | Chemistry : a European journal 2013-01, Vol.19 (3), p.1042-1057 |
|---|---|
| Main Authors: | , , , |
| Format: | Article |
| Language: | English |
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| Online Access: | Get full text |
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| Summary: | The chemistry of coinage metal bis(triflyl)imides of technological interest, CuNTf
2
and AgNTf
2
, their synthesis and complexes with excess of comparatively weakly coordinating NTf
2
−
as well as with ether, olefins, and the arene mesitylene are described. The existence of the solvent‐free pure phase [CuNTf
2
]
∞
has not been evidenced so far. Contrary to the literature, in which the preparation of [CuNTf
2
]
∞
is supposed to be carried out by reacting mesityl copper, [Cu(Mes)]
5
, and HNTf
2
, we found that in fact this reaction leads reproducibly to the interesting copper diarene sandwich complex [Cu(η
3
‐MesH)
2
][Cu(NTf
2
)
2
] (
1
) (MesH=1,3,5‐trimethylbenzene). The unexpectedly stable molecular etherate [Cu(Et
2
O)(NTf
2
)] (
2
) turned out to be the best precursor for CuNTf
2
having only an inert and easily exchangeable solvent ligand. The coordination mode of NTf
2
−
in
1
and
2
as well as in the hitherto unknown crystalline phase of [AgNTf
2
]
∞
(
3
) is described. The complex formation, which takes place when dissolving
2
or
3
in the room temperature ionic liquid (RTIL) [emim]NTf
2
([emim]
+
=1‐ethyl‐3‐methylimidazolium), has been studied. Furthermore, the reaction of
1
–
3
towards the diolefins 1,5‐cyclooctadiene (COD), 2,5‐norbornadiene (NBD) and isoprene (2‐methylbuta‐1,3‐diene) and towards ethylene has been investigated. The products
4
–
13
of these conversions have been isolated and fully characterized by NMR‐ and IR spectroscopies, mass spectrometry, and elemental‐ and XRD analyses. The potential of [Cu(η
3
‐MesH)
2
][Cu(NTf
2
)
2
] (
1
), [Cu(Et
2
O)(NTf
2
)] (
2
) and [AgNTf
2
]
∞
(
3
) as well as of [emim][M(NTf
2
)
2
] (M=Cu
4
, Ag
5
) as chemisorbers for ethylene was studied by NMR spectroscopy. |
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| ISSN: | 0947-6539 1521-3765 |
| DOI: | 10.1002/chem.201201740 |