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Selone-stabilized aryltellurenyl cations
Controlled bromination of a diarylditelluride, R 2 Te 2 (R = 2,6-dimethylphenyl) ( 6 ) in dichloromethane led to the formation of a Te II -Te IV mixed-valent tellurenyl bromide, RBr 2 TeTeR ( 7 ). A further reaction of 7 with 1,3-dibutylbenzimidazolin-2-selone, C 15 H 22 N 2 Se (L) ( 9 ), produced t...
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| Published in: | Dalton transactions : an international journal of inorganic chemistry 2016-01, Vol.45 (2), p.8458-8467 |
|---|---|
| Main Authors: | , , , |
| Format: | Article |
| Language: | English |
| Subjects: | |
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| Summary: | Controlled bromination of a diarylditelluride, R
2
Te
2
(R = 2,6-dimethylphenyl) (
6
) in dichloromethane led to the formation of a Te
II
-Te
IV
mixed-valent tellurenyl bromide, RBr
2
TeTeR (
7
). A further reaction of
7
with 1,3-dibutylbenzimidazolin-2-selone, C
15
H
22
N
2
Se (L) (
9
), produced the first selone adduct of the 2,6-dimethylphenyltellurenyl cation with the 2,6-dimethylphenyltellurium dibromide anion, [(2,6-Me
2
C
6
H
3
)Te(L)]
+
[(2,6-Me
2
C
6
H
3
)TeBr
2
]
−
(
10
). The red colored cationic adduct
10
is not stable in acetonitrile and disproportionated to give the selone adduct of 2,6-dimethylphenyltellurenyl bromide, [(2,6-Me
2
C
6
H
3
)Te(L)Br] (
11b
) and bis(2,6-dimethylphenyl)tellurium dibromide, [(2,6-Me
2
C
6
H
3
)
2
TeBr
2
], (
13
). The metathesis reaction of
11b
with AgBF
4
produced a stable dark red colored selone adduct of the 2,6-dimethylphenyltellurenyl cation with the BF
4
−
anion, [(2,6-Me
2
C
6
H
3
)Te(L)]
+
BF
4
−
(
15
). The selone adducts of aryltellurenyl halides,
i.e.
[(2,6-Me
2
C
6
H
3
)Te(L)X] (X = Cl, Br, I) (
11a-11c
), have been synthesized by a one-pot reaction of
6
with an equimolar mixture of
9
and 1,3-dibutylbenzimidazolin-2-dihaloselones, C
15
H
22
N
2
SeX
2
(
14a-14c
). Triphenylphosphine (PPh
3
), when treated with [(2,6-Me
2
C
6
H
3
)Te(L)X] (
11a-11c
), substitutes selone from the adduct to afford the triphenylphosphine adducts of aryltellurenyl halides, [(2,6-Me
2
C
6
H
3
)Te(PPh
3
)X] (
16a-16c
).
Selone (L) causes cleavage of the Te-Te bond of RTe(Br)
2
TeR (R = 2,6-Me
2
Ph) to give the first selone adduct of the 2,6-dimethylphenyltellurenyl cation with the 2,6-dimethylphenyltellurium dibromide anion, [(2,6-Me
2
C
6
H
3
)Te(L)]
+
[(2,6-Me
2
C
6
H
3
)TeBr
2
]
−
. |
|---|---|
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/c6dt01081d |