Journal of Fluorine Chemistry 112 "2001) 149±152
Oxidative per¯uoroorganylation methods in group 12±16 chemistry
The reactions of haloper¯uoroorganics and In and InBr,
a convenient new route to AgR "R CF , C F ) and
f
f
3
6 5
reactions of AgR with group 12±16 elements
f
*
Wieland E. Tyrra
Institut f uÈ r Anorganische Chemie, Universit aÈ t zu K oÈ ln, Greinstrasse 6, D-50939 K oÈ ln, Germany
Abstract
Per¯uoroiodo organics R I "Rf n-CnF2n1 "n 1, 2, 3, 4, 6), i-C F , C F ) and C F Br react with elemental indium in polyethers or
f
3
7
6
5
6 5
II
THF to give spectroscopic evidence for compounds of the general composition In R
f
X "X I, Br). All isolation attempts led to
Br in THF selectively and quantitatively yielded
In"C F )Br Á2THF which was structurally characterized. The reaction of In"C F )Br Á2THF and acetylacetone "Hacac) quantitatively gave
III
I
f 2 2 6 5
decomposition into In "R ) I and In I. In contrast, the reaction of In, 0.5Br and C F
6
5
2
6
5
2
the distorted octahedral molecule In"acac)Br
selectively prepared from AgF and Me SiR in several nitrile solvents. [PNP][Ag "CF
PNP][Ag "CF )Cl] is formed which is characterized by single crystal structure analysis. Besides its properties as a nucleophilic
2
Á2THF. Per¯uoroorganosilver"I) compounds Ag"R
f
) "Rf CF3, C
6 5
F ) are conveniently and
I
3
f
3
)
2
] "PNP bis"triphenylphosphoranyliden)ammo-
I
3
per¯uoroorganylating reagent, AgR
f
exhibits to be an excellent oxidative per¯uoroorganylation reagent in reactions with various elements
of groups 12±16 to give the corresponding per¯uoroorgano element compounds in moderate to excellent yields leaving elemental silver.
2001 Elsevier Science B.V. All rights reserved.
#
Keywords: Indium; Silicon; Silver; Per¯uoroalkyl; Penta¯uorophenyl; Oxidation; Group 12±16 elements
1
. Introduction
The use of per¯uoroorgano silver derivatives in halide
substitution reactions is documented [6±12]. Less is known
about their oxidative properties compared with the corre-
sponding mercury derivatives Hg"R ) , especially Hg"C F ) .
While per¯uoroiodo organics have been used mainly in
`high-temperature'' reactions since the early beginning of
`
f 2
6 5 2
per¯uoroalkylelement chemistry [1], less is known about the
synthetic use at lower temperature and especially in group
2. Results
1
3 chemistry.
All known per¯uoroalkyl indium compounds were acces-
2.1. Reactions of indium metal and
halogenoperfluoroorganics and consecutive reactions
sible exclusively via halide exchange reactions using
per¯uoroorgano cadmium compounds [2], while penta-
¯
routes using C F I, Hg"C F ) and Tl"C F ) Br [3±5].
uoro-phenyl derivatives have been prepared via oxidative
Per¯uoroiodo organics R I "R n-C F "n 1, 2, 3,
f
f
n
2n1
6
5
6
5 2
6
5 2
4, 6), i-C F , C F ) and C F Br and indium metal react in the
3 7 6 5 6 5
Per¯uoroorganosilver"I) compounds, AgR "Rf CnF2n1
f
stoichiometry 1:1 in polyethers such as glyme, diglyme,
tetraglyme or THF at ambient temperature to give com-
"
known for some time; however, the knowledge of AgCF is
n 2, 3, 4) [6] i-C F [6±8], t-C F [8] C F [9±12]) are
3
7
4
9
6
5
II
3
pounds of the general composition In R X "X I, Br
f
limited because of its tendency to decompose into elemental
"
Rf C6F5)). The reactions proceed selectively giving col-
I
silver and Ag [Ag "CF ) ] in the presence of metal ions
III
3
4
orless to pale yellow solutions.
stemming from the starting material Cd"CF ) Á2D
3
2
solvent
II
"
D unidentate donor) or Bi"CF ) [6,13,14].
R I InÀÀÀ! In ꢀR I
3
3
f
f
2
r:t:
solvent: polyther, THF
Rf : n-CnF2n1 ꢀn 1; 2; 3; 4; 6; i-C3F7; C6F5
*
Tel.: 49-221-470-3276; fax: 49-221-470-3276.
E-mail address: tyrra@uni-koeln.de "W.E. Tyrra).
0022-1139/01/$ ± see front matter # 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 " 0 1 ) 0 0 4 8 4 - 5