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Reactivity of Liquid Ammonia Solutions of the Zintl Phase K 12 Sn 17 towards Mesitylcopper(I) and Phosphinegold(I) Chloride
Abstract To gain more insight into the reactivity of intermetalloid clusters, the reactivity of the Zintl phase K 12 Sn 17 , which contains [Sn 4 ] 4− and [Sn 9 ] 4− cluster anions, was investigated. The reaction of K 12 Sn 17 with gold(I) phosphine chloride yielded K 7 [(η 2 ‐Sn 4 )Au(η 2 ‐Sn 4 )](...
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| Published in: | Chemistry : a European journal 2014-12, Vol.20 (50), p.16738-16746 |
|---|---|
| Main Authors: | , , , |
| Format: | Article |
| Language: | English |
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| Online Access: | Get full text |
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| Summary: | Abstract
To gain more insight into the reactivity of intermetalloid clusters, the reactivity of the Zintl phase K
12
Sn
17
, which contains [Sn
4
]
4−
and [Sn
9
]
4−
cluster anions, was investigated. The reaction of K
12
Sn
17
with gold(I) phosphine chloride yielded K
7
[(η
2
‐Sn
4
)Au(η
2
‐Sn
4
)](NH
3
)
16
(
1
) and K
17
[(η
2
‐Sn
4
)Au(η
2
‐Sn
4
)]
2
(NH
2
)
3
(NH
3
)
52
(
2
), which both contain the anion [(Sn
4
)Au(Sn
4
)]
7−
(
1 a
) that consists of two [Sn
4
]
4−
tetrahedra linked through a central gold atom. Anion
1 a
represents the first binary AuSn polyanion. From this reaction, the solvate structure [K([2.2.2]crypt)]
3
K[Sn
9
](NH
3
)
18
(
3
; [2.2.2]crypt=4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane) was also obtained. In the analogous reaction of mesitylcopper with K
12
Sn
17
in the presence of [18]crown‐6 in liquid ammonia, crystals of the composition [K([18]crown‐6)]
2
[K([18]crown‐6)(MesH)(NH
3
)][Cu@Sn
9
](thf) (
4
) were isolated ([18]crown‐6=1,4,7,10,13,16‐hexaoxacyclooctadiene, MesH=mesitylene, thf=tetrahydrofuran) and featured a [Cu@Sn
9
]
3−
cluster. A similar reaction with [2.2.2]crypt as a sequestering agent led to the formation of crystals of [K[2.2.2]crypt][MesCuMes] (
5
). The cocrystallization of mesitylene in
4
and the presence of [MesCuMes]
−
(
5 a
) in
5
provides strong evidence that the migration of a bare Cu atom into an Sn
9
anion takes place through the release of a Mes
−
anion from mesitylcopper, which either migrates to another mesitylcopper to form
5 a
or is subsequently protonated to give MesH. |
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| ISSN: | 0947-6539 1521-3765 |
| DOI: | 10.1002/chem.201404594 |