Structural isomerism in tris-tolyl halo-phosphonium and halo-arsonium tri-halides, [(CH3C6H4)3EX][X3], (E = P, As; X = Br, I)Electronic supplementary information (ESI) available: Discussion of anion-anion interactions in the structures of 1 and 2 (Fig. S1 and S2). Table of short non-classical hydrogen bonds (Table S1), and table of cation-cation packing arrangements and E E separations (Table S2). CCDC reference numbers 865498-865508. For ESI and crystallographic data in CIF or other electronic
The group 15 ligands ( o -CH 3 C 6 H 4 ) 3 P, ( m -CH 3 C 6 H 4 ) 3 P, ( p -CH 3 C 6 H 4 ) 3 P, Ph 3 As, ( o -CH 3 C 6 H 4 ) 3 As and ( p -CH 3 C 6 H 4 ) 3 As have been reacted with two equivalents of di-iodine or di-bromine to yield complexes of formula R 3 EX 4 (E = P, As; X = I, Br). These haloge...
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Zusammenfassung: | The group 15 ligands (
o
-CH
3
C
6
H
4
)
3
P, (
m
-CH
3
C
6
H
4
)
3
P, (
p
-CH
3
C
6
H
4
)
3
P, Ph
3
As, (
o
-CH
3
C
6
H
4
)
3
As and (
p
-CH
3
C
6
H
4
)
3
As have been reacted with two equivalents of di-iodine or di-bromine to yield complexes of formula R
3
EX
4
(E = P, As; X = I, Br). These halogenated group 15 compounds are ionic, [R
3
EX][X
3
] consisting of halo-phosphonium or halo-arsonium cations and trihalide anions. These adducts exhibit structural isomerism and may exist either as simple 1 : 1 ion pairs, [R
3
EX][X
3
], isomer (A), which display a weak X X interaction between cation and anion, or as a 2 : 1 complex, which consists of a [{R
3
EX}
2
X
3
]
+
cationic species made up of two [R
3
EX]
+
cations interacting with one [X
3
]
−
anion. The overall charge is balanced by a second [X
3
]
−
anion. These 2 : 1 species also exhibit structural isomerism due to subtle differences in the connectivity of the [{R
3
EX}
2
X
3
]
+
fragment, as the {R
3
EX}
+
units may either interact at the same end of the [X
3
]
−
ion, to give a Y-shaped motif, isomer (B), or at opposite ends, giving a Z-shaped motif, isomer (C). The type of structural isomer formed is related to the way in which [Ar
3
EX]
+
cations pack together
via
aryl embraces. Isomer (A) and (C) structures form chains of side-to-side, anti-parallel embracing cations. In (A) and (C) structures a square-like stacking motif of cations is observed. In contrast, isomer (B) structures feature side-to-side, parallel embracing cations, and do not exhibit the square motif.
The series of tolyl-substituted tri-halides, [Ar
3
EX][X
3
] (E = P, As), exhibit structural isomerism, existing either as 1 : 1 ion pairs, [Ar
3
EX][X
3
], or as a 2 : 1 complex, [{Ar
3
EX}
2
X
3
][X
3
], where the cationic fragment can either adopt a Y- or Z-shaped structure. |
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ISSN: | 1477-9226 1477-9234 |
DOI: | 10.1039/c2dt30235g |