Reactions of perfluorinated alkenyl-, alkynyl-, alkyltrifluoroborates, and selected hydrocarbon analogues with the halogenating agents Hal2 (Hal = F, Cl, Br), "brF" (BrF3-Br2 1:1), and ICl

Article abstract of DOI:10.1002/zaac.201100276

Reactions of [Bu₄N][RBF₃] [R = C_nF _2n+1CF=CF (cis, trans), CF₂=CF, CF₂=C(CF ₃), trans-C₄H₉CF=CF, trans-C₆H ₅CF=CF, C₄H₉CH=CH (cis, trans), CF ₃C≡C, and C₄H₉C≡C] with chlorine, bromine, BrF₃ + Br₂ (as equivalent of "BrF"), and ICl in solution (CH₂Cl₂, CHCl₃, CF ₃CH₂CF₂CH₃) led to 1, 2-addition of halogen and/or replacement of boron by halogen (halodeboration). The reaction of [Bu₄N][CF₃C≡CBF₃] with less than equimolar amounts of diluted fluorine (5 %) in 1, 1, 1, 3, 3-pentafluorobutane (PFB) showed only [Bu₄N][CF₃CF₂CF ₂BF₃] as fluorine addition product besides extensive fluorodeboration. Suspensions of the insoluble K[CF₂=CFBF ₃] salt reacted with Cl₂ and Br₂ in CH ₂Cl₂ giving preferentially products of halogen addition across the C=C bond. In reactions with ICl iododeboration with formation of CF₂=CFI occurred besides 1, 2-addition with formation of [CF ₂I-CFClBF₃]^-. The halodeboration reaction of[Bu₄N][trans-C₄H₉CF=CFBF₃] with Br₂, "BrF", and ICl, of K[trans-C₆H ₅CF=CFBF₃] with Br₂, and of [Bu ₄N][trans-C₄F₉CF=CFBF₃] with ICl proceeded stereospecifically. Copyright

Full text of DOI:10.1002/zaac.201100276

ARTICLE
DOI: 10.1002/zaac.201100276
Reactions of Perfluorinated Alkenyl-, Alkynyl-, Alkyltrifluoroborates, and
Selected Hydrocarbon Analogues with the Halogenating Agents Hal2 (Hal =
F, Cl, Br), “BrF” (BrF3–Br2 1:1), and ICl
Vadim V. Bardin,[a] Nicolay Yu. Adonin,[a,b] and Hermann-Josef Frohn*[c]
Dedicated to Professor Helge Willner on the Occasion of His 65th Birthday
Keywords: Alkenyltrifluoroborates; Alkynyltrifluoroborates; Alkyltrifluoroborates; 1,2-Halogen addition; Bromofluorination;
Halodeboration; Stereospecifity; NMR spectroscopy
Abstract. Reactions of [Bu4N][RBF3] [R = CnF2n+1CF=CF (cis, trans), fluorodeboration. Suspensions of the insoluble K[CF2=CFBF3] salt re-
CF2=CF, CF2=C(CF3), trans-C4H9CF=CF, trans-C6H5CF=CF,
C4H9CH=CH (cis, trans), CF3CϵC, and C4H9CϵC] with chlorine,
acted with Cl2 and Br2 in CH2Cl2 giving preferentially products of
halogen addition across the C=C bond. In reactions with ICl iodode-
bromine, BrF3 + Br2 (as equivalent of “BrF”), and ICl in solution boration with formation of CF2=CFI occurred besides 1,2-addition
(CH2Cl2, CHCl3, CF3CH2CF2CH3) led to 1,2-addition of halogen and/
with formation of [CF2I–CFClBF3]–. The halodeboration reaction of
or replacement of boron by halogen (halodeboration). The reaction [Bu4N][trans-C4H9CF=CFBF3] with Br2, “BrF”, and ICl, of K[trans-
of [Bu4N][CF3CϵCBF3] with less than equimolar amounts of diluted C6H5CF=CFBF3] with Br2, and of [Bu4N][trans-C4F9CF=CFBF3] with
fluorine (5%) in 1,1,1,3,3-pentafluorobutane (PFB) showed only ICl proceeded stereospecifically.
[Bu4N][CF3CF2CF2BF3] as fluorine addition product besides extensive
volved in platinum-catalyzed cross-coupling reactions with
Introduction
carbon electrophiles to give polyfluorobiphenyls or polyfluoro-
styrenes, respectively.[7–9] The nickel-catalyzed hydrodefluori-
nation of potassium pentafluorophenyltrifluoroborate with zinc
in aqueous DMF, DMA, or NMP displayed the unexpected
During the last decade we elaborated convenient protocols
for the synthesis of perfluorinated aryl-, alkenyl-, alkynyl-, alk-
yltrifluoroborates, and related analogues.[1,2] These borates
were mainly used as precursors for the corresponding organyl-
difluoroboranes by fluoride abstraction with boron trifluoride
or arsenic pentafluoride. Organyldifluoroboranes were the rea-
gents by choice to introduce the corresponding organyl groups
into hypervalent moieties of halogen fluorides and xenon fluo-
rides and allowed the synthesis of organyliodonium(III and
V),[3] organylbromonium(III),[4,5] and organylxenonium(II and
IV)[6] salts. Other reactivities of polyfluoroorganyl(fluoro)bor-
ates are only rarely investigated. Potassium polyfluorophenyl-
trifluoroborates and trifluoroethenyltrifluoroborates were in-
–
ortho-directing effect of the weakly coordinating BF3 substit-
uent and resulted in the formation of the 2,3,4,5-tetrafluo-
rophenyltrifluoroborate anion and 1,2,3,4-tetrafluorobenz-
ene.[10] We reported the carbon–boron bond cleavage in a
series of polyfluorinated organyltrifluoroborates and their hy-
drocarbon analogues (hydrodeboration reactions) with protic
acids of different strength[11] and had found the stereospecific
–
replacement of the BF3
group by hydrogen in
K[RCF=CFBF3] to form the corresponding polyfluoroalkenes
RCF=CFH. Fluorine addition across the C=C bond took place
when perfluoroalkenyltrifluoroborates were treated with xenon
difluoride in super acidic anhydrous hydrogen fluoride
(aHF).[12] When XeF2 was reacted with RCF=CFBF2 (R = H,
F, cis-CF3, cis-C2F5) in halocarbon solvents (CH2Cl2,
CF3CH2CF2CH3) xenonium salts [RCF=CFXe]X were formed
with two types of anions, X = [BF4]– and [RCF2–CF2BF3]–.[13]
Analogous products were observed in the reaction of XeF2
with CF2=CClBF2 in PFB,[14] whereas no organyltrifluorobor-
ate anions were formed in reactions of alkynyldifluoroboranes
RCϵCBF2 [R = CF3, C3F7, (CF3)2CF, CF3CF=CF (cis and
trans), C6F5, C4H9, (CH3)3C] with XeF2 under similar condi-
tions.[15]
* Prof. Dr. H.-J. Frohn
Fax: +49-203-379-2231
E-Mail: h-j.frohn@uni-due.de
[a] N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, SB
RAS
Acad. Lavrentjev Avenue 9
630090 Novosibirsk, Russia
[b] G. K. Boreskov Institute of Catalysis, SB RAS
Acad. Lavrentjev Avenue 5
630090 Novosibirsk, Russia
[c] Inorganic Chemistry Department
University of Duisburg-Essen
Lotharstrasse 1
47048 Duisburg, Germany
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201100276 or from the au-
thor.
In the course of systematic studies of perfluoroorganylboron
compounds, we investigated reactions of perfluorinated alk-
Z. Anorg. Allg. Chem. 2012, 638, (3-4), 565–579
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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V. V. Bardin, N. Y. Adonin, H.-J. Frohn
ARTICLE
1-enyltrifluoroborates, alk-1-ynyltrifluoroborates, and selected equivalent of fluorine by 19F NMR spectroscopy confirmed the
low-fluorinated and non-fluorinated analogues and alkyltri- multiple addition of fluorine across the CϵC bond forming
fluoroborates with halogenating agents of different nature [flu- [Bu4N][CF3CF2–CF2BF3]. The yield decreased slightly from
orine, chlorine, bromine, bromine trifluoride + bromine (1:1, 60 to 52% with the increase of conversion of
“BrF”), and iodine chloride] in halocarbon solvents (CH2Cl2, [Bu4N][CF3CϵCBF3] from 10 to 44%. Parallel the cleavage
CHCl3, CF3CH2CF2CH3).
of the carbon–boron bond proceeded, indicated by the ratio
For convenience, the substituent RЈ at C-2 in RЈC2F = C1FX [Bu4N][BF4] to [Bu4N][CF3CF2–CF2BF3], which grew from
molecules or ions is specified by cis or trans relative to the 0.56 to 0.90. The 19F NMR signals of the low boiling perfluo-
–
position of X = BF3 or Hal. The fluorine atoms in the rocarbon co-products as well as the resonances (11B, 19F) of
F2C=CXY moiety are specified by cis or trans relative to the the intermediate borate anion [CF3CF=CFBF3]– were not de-
–
position of X = BF3 and iodine (Y = F, CF3, CF2Cl).
tected (Scheme 2).
Halodeboration of [RBF3]– by dihalogen (Cl2, Br2) or inter-
halogen (ICl) should result in RCl, RBr, or RI and [BClF3]– or
[BBrF3]–, respectively. In all reactions with Cl2 and Br2 we
observed unambiguously only [BF4]– (19F, 11B). Principally,
equilibration by halide exchange may lead to [BF4]–:
4[BHalF3]– p 3[BF4]– + Ͻ[BHal4]–Ͼ. We did not obtain
NMR spectroscopic results, which agree with the reported data
of [BFnHal4–n]– (Hal = Cl, Br; n = 0–3).[16,17]
Scheme 2.
Results
Reactions of Tetrabutylammonium Perfluoroalkenyl- and
Perfluoroalkynyltrifluoroborates with Chlorine in
Halocarbon Solutions
Preparation of Tetrabutylammonium
Organyltrifluoroborates
A solution of [Bu4N][trans-C4F9CF=CFBF3] was saturated
with Cl2 (excess) and kept at approximately 20 °C for 24 h in
In our current study we compare the reactivities of organyl-
trifluoroborates towards selected halogenating agents in solu-
tion and on the surface of the salts. We chose tetrabutylammo-
nium organyltrifluoroborates as soluble salts in dichlorometh-
ane, chloroform, and 1,1,1,3,3-pentafluorobutane (PFB) and
potassium organyltrifluoroborates as insoluble salts in dichlo-
romethane. The tetrabutylammonium salts can be easily pre-
pared from the corresponding potassium salts by metathesis
with [Bu4N]X (X = Br, BF4) in MeCN in high yields
(Scheme 1). Compared with reactions of [Bu4N]OH in aque-
ous solution or related approaches[18] this procedure guarantees
dry products, which is important for the use of [Bu4N][RBF3]
salts under anhydrous conditions in subsequent reactions.
a
sealed tube. After evaporation of the volatiles,
[Bu4N][C4F9CFCl–CFClBF3] was obtained in 94% yield.
[Bu4N][CF2=CFBF3] reacted faster than [Bu4N][trans-
C4F9CF=CFBF3]. Bubbling of Cl2 (excess) into a solution
(≈0 °C) of [Bu4N][CF2=CFBF3] in dichloromethane resulted
in the total conversion of [Bu4N][CF2=CFBF3] within 0.5 h
with formation of [Bu4N][CF2Cl–CFClBF3], CF2=CFCl, and
[Bu4N][BF4] (molar ratio = 33:14:48) (Scheme 3).
Scheme 1.
Scheme 3.
[Bu4N][CF3CϵCBF3] reacted with an excess of Cl2 at ap-
proximately 20 °C slower than [Bu4N][trans-C4F9CF=CFBF3]
and [Bu4N][CF2=CFBF3]. Bubbling of Cl2 into a solution of
[Bu4N][CF3CϵCBF3] (≈0 °C) and reacting the mixture in a
Reaction of Tetrabutylammonium
Trifluoropropynyltrifluoroborate with Fluorine in PFB
Solution
Generally, the result of reactions of organic compounds with sealed tube (≈20 °C) for 24 h resulted in 62% conversion of
elemental fluorine is determined inter alia by a number of pro- [Bu4N][CF3CϵCBF3] and gave [Bu4N][CF3CCl=CClBF3]
cess-factors including the design of the reactor. In the current (54%, cis/trans = 46:54), [Bu4N][CF3CCl2–CCl2BF3] (4%),
study we bubbled fluorine diluted with nitrogen (5% v/v) [Bu4N][BF4] (42%), trace quantities of CF3CϵCCl,
through a stirred diluted solution of [Bu4N][CF3CϵCBF3] in CF3CCl2–CCl3, besides minor amounts of unknown products
PFB at ≈0 °C. Monitoring of the reaction with less than one (Scheme 4).
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1,2-Addition of Halogen and/or Replacement of Boron by Halogen
Scheme 4.
The further treatment of such a solution with a new excess
of chlorine (≈20 °C, sealed tube) for additional 33 h led to the
total consumption of [Bu4N][CF3CϵCBF3] and the majority of
[Bu4N][cis-CF3CCl=CClBF3]. The 11B and 19F NMR spectra
displayed the signals of [Bu4N][trans-CF3CCl=CClBF3]
(59%),
[Bu4N][cis-CF3CCl=CClBF3]
(Ͻ
3%),
[Bu4N][CF3CCl2–CCl2BF3] (8%), and [Bu4N][BF4] (26%),
besides several unknown compounds, which contained CF3
groups. The formation of CF3CCl=CCl2 was not detected.
Noteworthy, that partial chlorination of the tetrabutylammo-
nium cation proceeded, which was deduced from the 1H NMR
spectra of the reaction solution.
Scheme 5.
Scheme 6.
Reactions of Tetrabutylammonium Organyltrifluoroborates
with Bromine in Halocarbon Solutions
Solutions of [Bu4N][CnF2n+1CF=CFBF3] in CH2Cl2 reacted
with Br2 at approximately 20 °C slowly forming bromoper-
fluoroalkenes, -alkanes, and [Bu4N][BF4]. These reactions
were accompanied by cis/trans isomerization of the starting
borates. Perfluoro-1,2-dibromoalkyltrifluoroborates were not
detected as intermediates in such isomerization processes.
Thus, [Bu4N][cis-C2F5CF=CFBF3] and an equimolar amount
of Br2 gave after 21
h
an isomeric mixture of
[Bu4N][C2F5CF=CFBF3] (cis/trans = 72:28) besides smaller
quantities of C2F5CF=CFBr, C2F5CFBr–CFHBr, and
[Bu4N][BF4]. Heating of [Bu4N][C2F5CF=CFBF3] (cis/trans =
60:40) with Br2 (in excess) in CH2Cl2 (65–70 °C, 9 h) gave
[Bu4N][C2F5CF=CFBF3] (cis/trans = 75:25), C2F5CF=CFBr,
and [Bu4N][BF4]. Similarly, [Bu4N][trans-C4F9CF=CFBF3]
was partially isomerized (≈20 °C) after 66 h (cis/trans = 62:38)
and C4F9CF=CFBr (cis/trans = 17:83), and [Bu4N][BF4] were
formed. When the reaction was performed in the absence of
day-light, or [Bu4N][C4F9CF=CFBF3] was treated with Br2 at
65–70 °C for 11 h, the same products were obtained
(Scheme 5).
[Bu4N][CF2=CFBF3] reacted fast with an excess of Br2 to
yield [Bu4N][CF2Br–CFBrBF3], CF2=CFBr, and [Bu4N][BF4]
(Scheme 6). The formation of [Bu4N][CF2Br–CFBrBF3] was
the only example of bromine addition to the C=C bond of an
alk-1-enyltrifluoroborate observed in this study.
Scheme 7.
[Bu4N][C4H9CH=CHBF3] (cis/trans = 67:33) and an excess
of Br2 underwent bromodeboration in CHCl3 at approximately
20 °C to C4H9CH=CHBr (cis/trans = 63:37). Furthermore
C4H9CHBr–CH2Br and [Bu4N][BF4] were present. Hex-1-ene
was not detected, presumable due to a fast addition of bromine
with formation of C4H9CHBr–CH2Br (Scheme 8).
[Bu4N][trans-C4H9CF=CFBF3] reacted with Br2 (1 equiv.)
in CH2Cl2 to yield trans-C4H9CF=CFBr, trans-C4H9CF=CFH,
and [Bu4N][BF4]. The reaction in CHCl3 proceeded in a sim-
ilar way. When adding a second equivalent of Br2 trans-
C4H9CF=CFBr was partially isomerized to cis-C4H9CF=CFBr
and both isomers underwent partial addition of bromine to
form C4H9CFBr–CFBr2. Trans-C4H9CF=CFH added Br2 and
was completely converted to C4H9CFBr–CFHBr (Scheme 7).
Scheme 8.
The conversion of [Bu4N][CF3CϵCBF3] with Br2 (1 equiv.)
was 86% after 1 h at approximately 20 °C and resulted in
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567

V. V. Bardin, N. Y. Adonin, H.-J. Frohn
ARTICLE
[Bu4N][CF3CBr=CBrBF3] (cis/trans = 62:38), small amounts
of
CF3CBr=CBr2,
and
[Bu4N][BF4].
[Bu4N][CF3CBr=CBrBF3] and an excess of Br2 underwent
C–B bond splitting to alkene CF3CBr=CBr2. Bromine addition
across the C=C bond of [Bu4N][CF3CBr=CBrBF3] did not oc-
cur (Scheme 9).
Scheme 12.
The equimolar mixture of bromine trifluoride and bromine
is often described as an equivalent of “BrF” although the na-
ture of the key reactive species is not doubtless proven as well
as the mechanism of bromofluorination reactions with such
mixtures.[19–21] We prepared solutions of BrF3–Br2 (1:1) in
PFB and found that this solvent is not attacked at 20–25 °C at
least for 2 days. The 19F NMR spectrum displayed a broad
singlet at –23 ppm (Δν1/2 = 1512 Hz at 24 °C). This resonance
is in the same region as the signal of BrF3 in PFB (δ = –17.9;
s, Δν1/2 = 27 Hz).[4]
Scheme 9.
The interaction of BrF3–Br2 (1:1, ≈0.5 equiv. “BrF”) with a
PFB solution of [Bu4N][cis-C2F5CF=CFBF3] showed partial
isomerization of [Bu4N][C2F5CF=CFBF3] (cis/trans = 56:44)
and in a smaller quantity yield of [Bu4N][C2F5CFBr–CF2BF3],
C2F5CF=CFBr, and [Bu4N][BF4] (Scheme 13).
Bromine
[Bu4N][C4H9CϵCBF3] formed C4H9CϵCBr, C4H9CϵCH,
besides [Bu4N][BF4], C4H9CBr=CBr2, and trans-
C4H9CBr=CHBr, whereas cis-C4H9CBr=CHBr was only pres-
ent as a trace (Scheme 10). With an excess of bromine hexynes
C4H9CϵCH and C4H9CϵCBr were completely converted into
the alkenes trans-C4H9CBr=CHBr and C4H9CBr=CBr2,
respectively.
and
a
cold
CHCl3
solution
of
Scheme 13.
[Bu4N][CF2=CFBF3] reacted fast with BrF3–Br2 (1:1) in
PFB already at –15 °C to yield CF2=CFBr, C2F5Br, and
[Bu4N][BF4]. Polyfluorinated ethyltrifluoroborates were not
found (Scheme 14).
Scheme 10.
Noteworthy that [Bu4N][C6F13BF3] did not react with bro-
mine, while [Bu4N][C4H9BF3] reacted within 1 h under C–B
bond cleavage under bromo- and protodeboration (Scheme 11).
Scheme 14.
[Bu4N][trans-C4H9CF=CFBF3] reacted with BrF3–Br2 (1:1)
under cleavage of the C–B bond giving trans-C4H9CF=CFBr
and [Bu4N][BF4] (Scheme 15).
Scheme 11.
Scheme 15.
Reactions of Tetrabutylammonium Fluoroalkenyl- and
Fluoroalkynyltrifluoroborates with BrF3–Br2 (1:1,
Equivalent of “BrF”) in Halocarbon Solutions
Treatment of [Bu4N][CF3CϵCBF3] with BrF3–Br2
(1.2 equiv. “BrF”) in PFB resulted in 28% conversion of
In a preceding paper[4] we showed that the reaction of [Bu4N][CF3CϵCBF3] yielding [Bu4N][CF3CBr=CBrBF3],
[Bu4N][cis-C2F5CF=CFBF3] with BrF3 in PFB followed two [Bu4N][CF3CBr2–CF2BF3],
[Bu4N][CF3CBr2–CFBrBF3],
routes: (a) addition of BrF across the C=C bond with formation CF3CϵCBr, CF3CBr=CBr2, and [Bu4N][BF4]. The reaction
of [Bu4N][C2F5CFBr–CF2BF3] and (b) cleavage of the C–B with further BrF3–Br2 (4.8 equiv. “BrF”) led to the total con-
bond
with
formation
of
C2F5CF=CF2
(ratio version of [Bu4N][CF3CϵCBF3], the transformation of
59:41) and [Bu4N][CF3CBr=CBrBF3] to CF3CBr=CBr2, and an increased
yield of [Bu4N][CF3CBr2–CF2BF3] and of [Bu4N][BF4].
[Bu4N][C2F5CFBr–CF2BF3]/C2F5CF=CF2
[Bu4N][BF4] (Scheme 12).
=
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1,2-Addition of Halogen and/or Replacement of Boron by Halogen
[Bu4N][CF3CBr=CFBF3] was not detected as precursor of
[Bu4N][CF3CBr2–CF2BF3] and [Bu4N][CF3CBr2–CFBrBF3]
(Scheme 16).
Scheme 19.
[Bu4N][CF3CϵCBF3] underwent complete iododeboration
within 1 h forming CF3CϵCI and [Bu4N][BF4] (Scheme 20).
Scheme 16.
Scheme 20.
The 1:1 reaction of [Bu4N][C4H9BF3] with ICl in CH2Cl2
gave mainly iodobutane (iododeboration) and a significant
amount of butane (protodeboration) (Scheme 21).
Reactions of Tetrabutylammonium Organyltrifluoroborates
with Iodine Chloride in Halocarbon Solutions
Carbon–boron bond cleavage occurred fast in reactions of
perfluoroalkenyltrifluoroborates with iodine chloride in dichlo-
romethane at approximately 20 °C. Thus, [Bu4N][CF2=CFBF3]
underwent 75% conversion into CF2=CFI within 15 minutes.
The exhaustive formation of trans-C4F9CF=CFI from
[Bu4N][trans-C4F9CF=CFBF3] and ICl indicates the regiospe-
cifity of this process. Noteworthy, that the formation of
CF2=C(CF3)I (major) from [Bu4N][CF2=C(CF3)BF3] was ac-
companied by CF2=C(CF2Cl)I (minor) (Scheme 17).
Scheme 21.
Surface Reactions of Potassium Organyltrifluoroborates
with Halogenating Agents
In contrast to the well soluble tetrabutylammonium organyl-
trifluoroborate salts, the corresponding potassium salts are in-
soluble in CH2Cl2, CHCl3, and PFB (19F NMR). Nevertheless,
some of them reacted with halogenating agents in halocarbon
suspensions.
Bubbling of an excess of chlorine into a stirred suspension
of K[CF2=CFBF3] in CH2Cl2 at approximately 20 °C led to
salt K[CF2Cl–CFClBF3] and CF2Cl–CFCl2 (trace). In contrast,
a suspension of K[trans-C4F9CF=CFBF3] in 1,2-dichloroe-
thane did not react with chlorine under those conditions
(Scheme 22).
Scheme 17.
Treatment of [Bu4N][trans-C4H9CF=CFBF3] with 1 equiv.
of iodine chloride in CHCl3 led to the quantitative cleavage of
the carbon–boron bond with formation of trans-C4H9CF=CFI
and trans-C4H9CF=CFH (Scheme 18).
Scheme 18.
Besides [Bu4N][BF4], C4H9CH=CHI (cis/trans = 55:45) was
the main organic product of the 1:1 reaction of
[Bu4N][C4H9CH=CHBF3] (cis/trans = 67:33) with ICl. In ad-
Scheme 22.
No reaction took place when K[trans-C4F9CF=CFBF3] and
dition, C4H9CHCl–CH2I and C4H9CHCl–CH2Cl were found bromine were combined, even under more rigorous conditions
(Scheme 19).
(CCl4, sealed tube, Յ 95 °C, 14 h) (Scheme 22).
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V. V. Bardin, N. Y. Adonin, H.-J. Frohn
ARTICLE
The reaction of K[CF2=CFBF3] (suspension in CH2Cl2) K[CF2I–CFClBF3], the 19F NMR spectrum showed an admix-
with bromine (1 equiv.) at 0 °C gave K[CF2Br–CFBrBF3] ture of an additional borate, presumably, K[FC(O)–CFClBF3]
(93% isolated yield) and
a minor amount (5%) of (Scheme 26).
CF2Br–CFBr2. Irradiation combined with more rigorous condi-
tions did not have a positive effect on the result (Scheme 23).
Scheme 26.
Discussion
Reactions of alkenyl- and alkynyltrifluoroborate salts with
halogenating agents in halocarbon solvents can principally pro-
ceed on two paths, (a) addition across the C=C or CϵC bond
and (b) under carbon–boron bond cleavage. The C–B bond
of alkyltrifluoroborates remained intact on path (a) under the
reaction conditions (halocarbons, mostly ambient temperature),
whereas the products of path (b) could underwent further con-
versions. A detailed analysis of these secondary processes was
out of the scope of our current investigation.
The reactions of alkenyl- and alkynyltrifluoroborate salts
with halogenating agents in halocarbon solvents were some-
times complex. They can be summarized using simplified de-
scriptions:
Scheme 23.
K[trans-C4F9CF=CFBF3] in a halocarbon suspension did
not react with bromine (CH2Cl2, ≈20 °C, 20 h; CCl4, Յ95 °C,
14 h) as shown in Scheme 22. In contrast, exclusively carbon–
boron bond cleavage took place in surface reactions of CH2Cl2
suspensions of K[trans-C4H9CF=CFBF3] and K[trans-
C6H5CF=CFBF3] with bromine. The primarily formed bromo-
alkenes C4H9CF=CFBr and trans-C6H5CF=CFBr added in a
second step bromine across the C=C bond yielding the tribro-
modifluoroalkanes C4H9CFBr–CFBr2 and C6H5CFBr–CFBr2,
respectively, which were the major products (Scheme 24).
1. [Bu4N][CF3CϵCBF3] reacted with fluorine preferred by
fluorine addition across the CϵC triple bond and in a subse-
quent faster step across the C=C double bond.
[Bu4N][CF3CF=CFBF3] could not be observed as an interme-
diate product of this reaction sequence. On an alternative chan-
nel the C–B bond was cleaved. [Bu4N][BF4] was a characteris-
tic final product of the second channel. The relative contri-
bution of the first channel (fluorine addition to multiple C–C
bonds, a typical radical reaction) was estimated to 50–60%.
2. The reaction of [Bu4N][trans-C4F9CF=CFBF3] with chlo-
rine gave [Bu4N][C4F9CFCl–CFClBF3] in 94% yield. Re-
placement of R = C4F9 in [Bu4N][RCF=CFBF3] by the less
electron-withdrawing substituent R = F led to an increasing
contribution of the C–B bond cleavage (Scheme 3). In contrast,
in the surface reaction of K[CF2=CFBF3] with Cl2 the addition
of chlorine to the double bond was the favored reaction
channel (65% yield of K[CF2Cl–CFClBF3]). In CH2Cl2
Scheme 24.
Astonishing,
that
the
alkynyltrifluoroborate
salt
K[CF3CϵCBF3] did not react with a large excess of bromine
in CH2Cl2-suspension within 36 h (≈20 °C) (Scheme 25).
solution
[Bu4N][CF3CϵCBF3] showed that 1,2-dichlorination was
preferred over C–B bond cleavage (ratio
the
perfluoropropynyltrifluoroborate
salt
[Bu4N][CF3CCl=CClBF3]/[Bu4N][BF4] = 56:44 at 62% con-
version of [Bu4N][CF3CϵCBF3] and 71:29 at 100% conver-
sion of [Bu4N][CF3CϵCBF3]). In addition it is worth men-
tioning that with progressive conversion the trans isomer of
[Bu4N][CF3CCl=CClBF3] increased. The parallel trend of
C–B bond cleavage and diminishing of [Bu4N][cis-
Scheme 25.
When a suspension of K[C4H9BF3] in CH2Cl2 was stirred CF3CCl=CClBF3] with progressive conversion leads to the
with an excess of bromine (≈20 °C, 6 h) only Ͻ5% conversion conclusion that the C–B bond cleavage of [Bu4N][cis-
of K[C4H9BF3] was found and traces of C4H9Br and C4H10 CF3CCl=CClBF3]
is
favored
over
[Bu4N][trans-
were observed (Scheme 25).
CF3CCl=CClBF3]. The consecutive chlorination reaction of
A CH2Cl2-suspension of salt K[CF2=CFBF3] was treated [Bu4N][CF3CCl=CClBF3] with Cl2 proceeded very slowly.
with ICl and CF2=CFI was formed together with K[CF2I– This reactivity is different to the second fluorination step of
CFClBF3]. After working-up the products and isolation of [Bu4N][CF3CϵCBF3].
570
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© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2012, 565–579

1,2-Addition of Halogen and/or Replacement of Boron by Halogen
3. Reactions of [Bu4N][CnF2n+1CF=CFBF3] with bromine caused the addition of Iδ+ to C-2 and K[CF2I–CFClBF3] was
obtained.
7. We can make some conclusions, e.g., for reactions with
occurred slowly and resulted in a complete C–B bond cleav-
age. Even [Bu4N][CF2=CFBF3] reacted predominantly under
C–B bond cleavage. Besides the bromine addition product,
[Bu4N][CF2Br–CFBrBF3], was formed. In contrast,
K[CF2Br–CFBrBF3] was obtained in up to 93% isolated
yield from K[CF2=CFBF3] in the surface reaction in
bromine concerning electronic and steric influences based on
a limited number of experiments: (a) The electrophilic attack
of Br2 on C-1 of the alkenylborate anion [RCF=CFBF3]– is
favored in case of less electron-withdrawing groups R. (b) The
trans isomer of isomeric mixtures of [RFCF=CFBF3]– (RF =
C2F5, C4F9) underwent a faster C–B cleavage than the cis iso-
mer, which can be deduced to a steric protection of C-1 in
case of the cis isomer. (c) Organyltrifluoroborate anions can
be formally considered as adducts of the organyl anion and
BF3. This simplification is helpful to rationalize the different
reactivity e.g. of the anions [CF3CϵCBF3]– and
[C4H9CϵCBF3]– in solution. The organyl group of the latter
has a more carbanionic character, which favors in reactions
with bromine the formation of C4H9CϵCBr (nucleophilic at-
tack on the electrophile Br2) and C4H9CϵCH (one-electron
oxidation followed by radical attack on C–H bonds). This con-
sideration is additionally supported by the experimental results
of alkyltrifluoroborates and bromine. The [C6F13BF3]– anion
has a weak C–B bond caused by the repulsion of the partial
positive charge on the adjacent carbon and boron atoms. But
the weak bond is not accompanied by high reactivity. In con-
trast, a nucleophilic attack on Br2 did not proceed because of
the low nucleophilicity of the carbanion. The opposite situation
can be discussed for the [C4H9BF3]– anion in reactions with
Br2, which gave C4H9Br and C4H10, the suspected products
for interactions of the corresponding carbanion and bromine.
8. Potassium organyltrifluoroborates are insoluble in halo-
carbons (proven by 19F NMR spectroscopy). In the solid the
anions have a fixed orientation on the surface and are less
activated by collisions with solvent molecules as in diluted
solutions. In conclusion the number of reaction channels is
reduced. In our case the addition across the double bond of the
alkenyl group became preference over the C–B bond cleavage.
CH2Cl2.
[Bu4N][CF3CϵCBF3]
and
bromine
gave
[Bu4N][CF3CBr=CBrBF3] (92% yield) in CH2Cl2 solution. It
is important to mention that [Bu4N][CF3CBr=CBrBF3] reacted
with a further equivalent of bromine slowly under complete
C–B bond cleavage. In case of alkyltrifluoroborates the C–B
bond cleavage with bromine depended on the nature of the
alkyl group: the perfluoroalkyl-B bond was inert, whereas the
non-fluorinated alkyl-B bond underwent a fast cleavage in re-
actions with bromine (bromodeboration and protodeboration).
[Bu4N][trans-C4H9CF=CFBF3] reacted significantly faster
with bromine than [Bu4N][CnF2n+1CF=CFBF3] salts predomi-
nantly under bromodeboration and in a lower extent under pro-
todeboration. With an excess of bromine the [trans-
C4H9CF=CFBF3]– anion underwent partial isomerization.
H–Hal – necessary for protodeboration – may stem from
halogen attacks on C–H bond in the solvent or the cation. A
further radical channel is discussed under 7.
A plausible explanation of the cis/trans isomerization of alk-
enyl groups in alkenyltrifluoroborate anions is based on ad-
dition of a halogen electrophile to C=C followed by C–C bond
rotation and elimination of the electrophile.
4. When [Bu4N][cis-C2F5CF=CFBF3] reacted with ca.
0.5 equiv. of “bromine fluoride” (BrF3 + Br2, 1:1), bromofluo-
rination (addition of Brδ+ at C-2) of the C=C bond was the
main reaction channel. In a lower extend bromofluorination
proceeded also in case of [Bu4N][CF3CϵCBF3] (two times)
and
[Bu4N][CF3CBr=CBrBF3].
In
contrast,
salts
[Bu4N][RCF=CFBF3] (R = F, trans-C4H9) formed no 2-bromo-
1-fluoroalkyltrifluoroborates. Instead of BrF addition to the
C=C bond bromodeboration proceeded with BrF.
5. Reactions of soluble tetrabutylammonium borates
[Bu4N][RBF3] (R = RFCF=CF, RFCϵC, or trans-C4H9CF=CF)
with ICl underwent exclusively carbon–boron bond cleavage
to yield RI. However, the surface reaction of K[CF2=CFBF3]
with ICl led to equal amounts of CF2=CFI and
K[CF2I–CFClBF3] (Iδ+ adds to C-2 of the C=C bond).
6. Some of the CH2Cl2 insoluble potassium organyltrifluoro-
borates showed no reaction with halogenating agents under
reasonable conditions: K[trans-C4F9CF=CFBF3]/Cl2, K[trans-
C4F9CF=CFBF3]/Br2, K[CF3CϵCBF3]/Br2, and K[C4H9BF3]/
Br2. Insoluble K[CF2=CFBF3] underwent with Cl2 or Br2 pre-
ferentially halogen addition across the C=C bond. When one of
the electron-withdrawing F2 atoms was substituted by a non-
fluorinated alkyl or phenyl group bromodeboration proceeded
followed by a fast bromine addition across the C=C bond.
K[CF2=CFBF3] showed in reactions with dipolar ICl both re-
action channels: ICl addition and iododeboration. In agreement
with the polarity of the C–B σ bond Iδ+ was added to C-1 and
Experimental Section
Materials and Measurements
The NMR spectra were recorded with the Bruker spectrometers
AVANCE 300 (1H at 300.13 MHz, 19F at 282.40 MHz, 11B at
96.29 MHz, 13C at 75.47 MHz) and AVANCE 600 (11B at
192.60 MHz). The chemical shifts are referenced to TMS (1H, 13C),
BF3·OEt2/CDCl3 (15% v/v) (11B), and CCl3F [19F, with C6F6 as sec-
ondary reference (–162.9 ppm)]. The IR spectra were recorded with a
Bruker Vector 22 spectrometer and the high resolution mass spectra
with a Finnigan MAT 8200 instrument (EI mode).
The composition of the reaction mixtures and the yields of products
were determined by 1H or 19F NMR spectroscopy using the internal
integral standards C6H5CF3, C6F6, or [Bu4N][PF6].
1,1,1,3,3-Pentafluorobutane (PFB) (Solvay Fluor und Derivate GmbH)
was stored over molecular sieves 3 Å before use. Acetonitrile and
dichloromethane were purified and dried using described procedures
[22]. Chloroform, carbon tetrachloride, and 1,2-dichloroethane were
CF2=CFI was formed and the polarity of the C=C π bond washed with water (twice), dried with CaCl2, stirred with P4O10 for
Z. Anorg. Allg. Chem. 2012, 565–579
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de 571

V. V. Bardin, N. Y. Adonin, H.-J. Frohn
ARTICLE
several hours and distilled off. The purified solvents were stored over
molecular sieves (3 Å) before use. [Bu4N][BF4] (Fluka), [Bu4N]Br [q (1:1:1:1), J(F, B) = 42 Hz, 3F, BF3] ppm.
(Fluka), and ICl (Fluka) were used as supplied. Chlorine (n mmol) was
–55.0 (m, 3F, CF3), –69.5 (m, 1F, F2trans), –78.2 (m, 1F, F2cis), –138.0
1
Preparation of [Bu4N][trans-C4F9CF=CFBF3]: The salt (485 mg,
82%) was obtained from [Bu4N]Br (322 mg, 1.0 mmol) and K[trans-
prepared by addition of 37% hydrochloric acid (0.8n mL) to KMnO4
(0.8n mmol, 126n mg)[23] in a slow stream of argon. Crude chlorine in
argon was passed through calcinated CaO in a column (D = 0.5 cm,
L = 3 cm) to remove HCl and moisture. Bromine was washed with
concentrated H2SO4 and distilled over P4O10. Bromine trifluoride was
prepared by bubbling of fluorine (25% v/v in nitrogen) into dry bro-
mine at 8–20 °C. The organyltrifluoroborate salts [Bu4N][cis-
C4F9CF=CFBF3] (388 mg, 1.0 mmol) in MeCN (11 mL) as described
1
above. 11B NMR (CH2Cl2): δ = –0.4 [qd, J(B, F) = 38, 2J(B, F1) =
27 Hz, BF3]. 19F NMR (CH2Cl2): δ = –81.3 (3F, F6), –116.5 (2F, F3),
–124.7, –126.4 (4F, F4,5), –143.9 [q (1:1:1:1), 1J(F, B) = 42 Hz, 3F,
BF3], –153.3 (1F, F1), –177.6 (1F, F2) ppm.
C2F5CF=CFBF3],[4]
K[trans-C4H9CF=CFBF3],
K[CF2=CFBF3],
K[trans-C4F9CF=CFBF3],
K[cis-
Preparation of [Bu4N][CF3CϵCBF3]: The salt (404 mg, 88%) was
K[trans-C6H5CF=CFBF3],
prepared
from
[Bu4N][BF4]
(374 mg,
1.13 mmol)
and
C2F5CF=CFBF3],[24] K[CF2=C(CF3)BF3],[14] K[CF3CϵCBF3],[25]
K[C4H9CH=CHBF3], K[C4H9BF3],[11] and K[C6F13BF3][4] were syn-
thesized using published procedures. Solubilities of selected organyl-
fluoroborate salts in different solvents are given in Table S1 (Support-
ing Information).
K[CF3CϵCBF3] (235 mg, 1.17 mmol) in MeCN (3.5 mL) as described
above. 11B NMR (PFB): δ = –2.7 [q, 1J(B, F) = 31 Hz, BF3]. 11B
NMR (CH2Cl2): δ = –3.3 [q, 1J(B, F) = 32 Hz, BF3]. 19F NMR (PFB):
1
δ = –47.4 (s, 3F, F3), –132.8 [q (1:1:1:1), J(F, B) = 31 Hz, 3F, BF3].
19F NMR (CH2Cl2): δ = –49.0 (s, 3F, F3), –136.0 [q (1:1:1:1), 1J(F,
B) = 32 Hz, 3F, BF3].
The synthesis of K[C4H9CϵCBF3] was performed according to ref.[26]
.
K[C4H9CϵCBF3]. 1H NMR (CD3CN): δ = 2.12 [t, 3J(H3, H4) = 7 Hz,
2 H, H3], 1.42 (m, 2CH2), 0.91 [t, 3J(H6, H5) = 7 Hz, 3 H, H6]. 19F
Preparation
of
[Bu4N][trans-C4H9CF=CFBF3]:
Salt
K[C4H9CF=CFBF3] (392 mg, 1.74 mmol) was suspended in MeCN
(5 mL) and [Bu4N]Br (561 mg, 1.74 mmol) was added in one portion.
The suspension was stirred for 1 h. The mother liquor was separated
by sequential centrifugation and decantation and evaporated under re-
duced pressure. The colorless viscous oil was pumped in a vacuum-
desiccator with Sicapent® and gave a solid product (707 mg, 95%).
1H NMR (CDCl3): δ = 2.24 [dtt, 3J(H3, F2) = 24, 4J(H3, H5) = 7,
4J(H3, F1) = 7 Hz, 2 H, H3], 1.35 (m, 2CH2), 0.92 [t, 3J(H6, H5) =
7 Hz, 3 H, H6] [trans-C4H9CF = CFBF3]–; 3.14 (m, 4CH2), 1.54 (m,
1
NMR (CD3CN): δ = –133.6 [q (1:1:1:1), J(F, B) = 38 Hz, 3F, BF3].
1
11B NMR (CD3CN): δ = –1.9 [q, J(B, F) = 38 Hz, BF3]. 19F NMR
([D6]DMSO): δ = –131.1 [broadened q (1:1:1:1), 3F, BF3]. 13C{19F}
NMR ([D6]DMSO): δ = 92.4 (br. m, C-1), 90.3 (m, C-2), 31.8 [t,
1
1J(C-4, H4) = 125 Hz, C-4], 22.2 [t, J(C-5, H5) = 124 Hz, C-5], 19.3
1
[t, J(C-3, H3) = 128 Hz, C-3], 14.2 [q, 1J(C-6, H6) = 125 Hz, C-6].
NMR spectroscopic data in [D6]acetone (cf.[26,27]) are given in
Table S2 (Supporting Information).
4CH2), 1.35 (m, 4CH2), 0.92 [t, 3J(H4, H3)
= 7 Hz, 4CH3]
Manipulations with fluorine and BrF3 were performed in FEP (block
copolymer of tetrafluoroethylene and hexafluoropropylene) or PFA
(block copolymer of tetrafluoroethylene and perfluoroalkoxytrifluoro-
ethylene) equipment in an atmosphere of dry argon. The NMR spectra
of BrF3 and BrF3–Br2 solutions were measured in FEP inliners (Di =
3.50Ϯ0.05 mm, Do = 4.10Ϯ0.05 mm).
[(C4H9)4N]+. 11B NMR (CDCl3): δ = 0.7 (br. s, Δν1/2 = 149 Hz, BF3).
3
3
19F NMR (CDCl3): δ = –158.6 [dtq J(F2, F1) = 119, J(F2, H3) = 24,
4J(F2, BF) = 10 Hz, 1F, F2], –172.5 [d 3J(F1, F2) = 119 Hz, 1F, F1],
–143.6 [broadened q (1:1:1:1), 3F, BF3].
Preparation of [Bu4N][C4H9CH=CHBF3]: The salt (664 mg, 90%)
was obtained as a colorless viscous oil from [Bu4N]Br (603 mg,
1.87 mmol) and K[C4H9CH=CHBF3] (cis/trans = 69:31) (355 mg,
1.87 mmol) in MeCN (15 mL) as described above. 1H NMR (CDCl3):
Preparation of Tetrabutylammonium
Organyltrifluoroborates
3
3
δ = 5.75 [dt, J(H2, H1) = 18, J(H2, H3) = 6 Hz, 1 H, H2], 5.41 [d,
3J(H1, H2) = 18 Hz, 1 H, H1], 2.03 (m, 2 H, H3), 1.57 (m, CH2), 1.25
(m, CH2), 0.80 (m, 3 H, H6) [trans-C4H9CH=CHBF3]–; 5.65 (m, 1 H,
H2), 5.31 [dq 3J(H1, H2) = 13, 3J(H1, BF) = 6 Hz, 1 H, H1], 2.19
(m, 2 H, H3), 1.57 (m, CH2), 1.25 (m, CH2), 0.80 (m, 3 H, H6) [cis-
C4H9CH=CHBF3]–; 3.20 (m, 4CH2), 1.57 (m, 4CH2), 1.37 (m, 4CH2),
Preparation of [Bu4N][CF2=CFBF3]: A solution of [Bu4N][BF4]
(0.99 g, 3.0 mmol) in MeCN (5 mL) was added to a solution of
K[CF2=CFBF3] (575 mg, 3.0 mmol) in MeCN (10 mL). The resulting
suspension was stirred for 1 h. The mother liquor was separated from
K[BF4] by sequential centrifugation and decantation. Finally the sol-
vent was evaporated under reduced pressure. The colorless viscous
product was dried in a vacuum desiccator with Sicapent® and gave a
white solid (1.13 g, 2.27 mmol) (yield 92%). 11B NMR (CD2Cl2): δ =
0.5 [ddq 2J(B, F1) = 25, 3J(B, F2trans) = 7, 1J(B, F) = 41 Hz, BF3].
13C{19F2cis,2trans} NMR (CD3CN): δ = 160.4 (C-2), 136.6 [q (1:1:1:1)
d, 1J(C-1, B) = 100, 1J(C-1, F1) = 220 Hz, C-1] ([CF2=CFBF3]–); 59.2,
24.2, 20.2, 13.5 ([(C4H9)4N]+). 19F NMR (CD2Cl2): δ = –102.4 [d,
2J(F2trans, F2cis) = 91 Hz, 1F, F2trans], –125.1 [dd, 2J(F2cis, F2trans) = 91,
3J(F2cis, F1) = 112 Hz, 1F, F2cis], –144.3 [q (1:1:1:1), 1J(F, B) = 41 Hz,
3
0.93 [t, J(H4, H3) = 7 Hz, 4CH3] [(C4H9)4N]+. 11B NMR (CDCl3): δ
= 2.9 [q, 1J(B, F) = 58 Hz, BF3]. 19F NMR (CDCl3): δ = –135.6
[broadened q (1:1:1:1), 3F, BF3] [cis-C4H9CH=CHBF3]–; –140.9
[broadened q (1:1:1:1), 3F, BF3] [trans-C4H9CH=CHBF3]–.
Preparation of [Bu4N][C4H9CϵCBF3]: The salt (650 mg, 94%) was
obtained as
a colorless viscous oil from [Bu4N]Br (570 mg,
1.77 mmol) and K[C4H9CϵCBF3] (333 mg, 1.77 mmol) in MeCN
(10 mL) as described above. 1H NMR (CDCl3): δ = 2.03 [t, 3J(H3,
H4) = 7 Hz, 2 H, H3], 1.36 (m, 2CH2), 0.78 [t, 3J(H6, H5) = 7 Hz,
3 H, H6] [C4H9CϵCBF3]–; 3.19 (m, 4CH2), 1.56 (m, 4CH2), 1.36 (m,
4CH2), 0.92 [t, 3J(H4, H3) = 7 Hz, 4CH3] [(C4H9)4N]+. 11B NMR
(CDCl3): δ = –1.6 (br. s, Δν1/2 = 126 Hz, BF3). 19F NMR (CDCl3): δ
= –133.9 [broadened q (1:1:1:1), 3F, BF3].
3
3F, BF3], –196.3 [d, J(F1, F2cis) = 112 Hz, 1F, F1] ppm.
Preparation of [Bu4N][CF2=C(CF3)BF3]: The salt (310 mg, 70%)
was obtained from [Bu4N][BF4] (288 mg, 0.87 mmol) and
K[CF2=C(CF3)BF3] (207 mg, 0.87 mmol) in MeCN (2 mL) as de-
scribed above. 13C {19F} NMR (CD2Cl2): δ = 157.7 (F2C=), 126.8
Preparation of [Bu4N][C4H9BF3]: The salt (710 mg, 91%) was pre-
(F3CC=), 84.9 [q (1:1:1:1), 1J(C-1, B) = 80 Hz, C-1] ([CF2=C(CF3) pared as a colorless viscous oil from [Bu4N]Br (680 mg, 2.13 mmol)
BF3]–); 58.9, 23.9, 19.9, 13.0 ([(C4H9)4N]+). 19F NMR (CD2Cl2): δ =
and K[C4H9BF3] (349 mg, 2.13 mmol) in MeCN (10 mL) as described
572 www.zaac.wiley-vch.de
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2012, 565–579

1,2-Addition of Halogen and/or Replacement of Boron by Halogen
1
3
2
above. H NMR (CDCl3): δ = 1.22 (m, 2CH2), 0.78 [t, J(H4, H3) =
289 Hz, 1F, F5A], –125.3 [md J(F5B, F5A) = 289 Hz, 1F, F5B], –127.3
7 Hz, 3 H, H4], 0.14 (m, 2 H, H1), [C4H9BF3]–; 3.17 (m, 4CH2), 1.55 (m, 1F, F1), –135.1 (m, 1F, F2), –148.0 [q (1:1:1:1), J(F, B) = 36 Hz,
1
(m, 4CH2), 1.36 (m, 4CH2), 0.92 [t, 3J(H4, H3) = 7 Hz, 4CH3] 3F, BF3] (diastereomer A); –80.0 [tt, J(F6, F5) = 3 Hz, t J(F6, F4) =
4
3
[(C4H9)4N]+. 11B NMR (CDCl3): δ = 5.4 (br. s, Δν1/2 = 218 Hz, BF3). 10 Hz, 3F, F6], –113.4 [md 2J(F3A, F3B) = 286 Hz, 1F, F3A], –115.0
19F NMR (CDCl3): δ = –141.1 [broadened q (1:1:1:1), 3F, BF3].
[md 2J(F3B, F3A) = 286 Hz, 1F, F3B), –118.0 (md 2J(F4A, F4B) =
2
298 Hz, 1F, F4A), –119.9 (md J(F4B, F4A) = 298 Hz, 1F, F4B], –121.7
[md 2J(F5A, F5B) = 318 Hz, 1F, F5A], –124.8 [md 2J(F5B, F5A) =
318 Hz, 1F, F5B], –124.8 (m, 1F, F1), –134.0 (m, 1F, F2), –149.7 [q
(1:1:1:1), 1J(F, B) = 41 Hz, 3F, BF3] (diastereomer B); –80.0 [tt, 4J(F6,
F5) = 3, 3J(F6, F4) = 10 Hz, 3F, F6], –111.3 [md 2J(F3A, F3B) = 286 Hz,
1F, F3A], –113.5 [md 2J(F3B, F3A) = 287 Hz, 1F, F3B], –117.2 [md
Preparation of [Bu4N][C6F13BF3]: The salt (336 mg, 89%) was pre-
pared as a colorless viscous oil from [Bu4N]Br (193 mg, 0.60 mmol)
and K[C6F13BF3] (292 mg, 0.68 mmol) in MeCN (5 mL) as described
1
above. H NMR (CDCl3): δ = 3.20 (m, 4CH2), 1.55 (m, 4CH2), 1.36
3
(m, 4CH2), 0.90 [t, J(H4, H3) = 7 Hz, 4CH3] [(C4H9)4N]+. 19F NMR
(CDCl3): δ = –80.0 [t, 4J(F6, F4) = 10 Hz, 3F, F6], –121.9, –122.6,
2
2J(F4A, F4B) = 293 Hz, 1F, F4A}, –119.9 [md J(F4B, F4A) = 293 Hz,
–123.0 (3CF2), –126.1 (m, 2F, F5), –131.8 (m, 2F, F1), –149.6 [q
1F, F4B], –123.4 (m, 1F, F1), –124.8 (m, 2F, F5), –134.7 (m, 1F, F2),
1
1
(1:1:1:1), J(F, B) = 40 Hz, 3F, BF3].
–148.1 [q (1:1:1:1), J(F, B) = 36 Hz, 3F, BF3] (diastereomer C) (ratio
A:B:C = 57:31:12). 19F NMR spectroscopic data in CDCl3 are given
in Table S2 (Supporting Information).
Reaction of [Bu4N][CF3CϵCBF3] with Fluorine in PFB
Solution
Reaction
of
[Bu4N][CF2=CFBF3]:
A
solution
of
[Bu4N][CF2=CFBF3] (0.21 mmol) in CH2Cl2 (1 mL) and CD2Cl2
(0.2 mL) in a glass tube was cooled to 0 °C (ice bath) in an atmosphere
of dry argon and chlorine (0.3 mmol) in argon was slowly bubbled
into the solution for 30 min. The colorless solution contained
[Bu4N][CF2Cl–CFClBF3] (0.07 mmol, 33%), CF2=CFCl (0.03 mmol,
14%), and [Bu4N][BF4] (0.10 mmol, 48%). [Bu4N][CF2=CFBF3] was
totally consumed (11B and 19F NMR).
A solution of [Bu4N][CF3CϵCBF3] (117 mg, 0.29 mmol) in PFB
(2 mL) was charged into an 8 mm i. d. FEP trap equipped with a mag-
netic stir bar and cooled to 0 °C. Less than the equivalent amount of
fluorine (0.19 mmol) diluted with nitrogen (5% v/v) was bubbled in
3 steps into the cold stirred solution. After 15 min the reaction was
interrupted, the solution was flushed with dry argon, and a probe was
taken in
[Bu4N][CF3CϵCBF3]
a
cold (0 °C) FEP inliner. The solution contained
(0.260 mmol, 10% conversion),
[Bu4N][CF2Cl–CFClBF3]: 11B NMR (CH2Cl2 + CD2Cl2): δ = 0.0 [dq
[Bu4N][C3F7BF3] (0.018 mmol, 60%) (identified by 19F NMR[28]),
and [Bu4N][BF4] (0.010 mmol, 33%). The probe was combined with
the main reaction solution and the treatment with fluorine was con-
tinued. Similarly as described before, the composition of the reaction
solution was determined after 30 min {[Bu4N][CF3CϵCBF3]
(0.230 mmol) (21% conversion), [Bu4N][C3F7BF3] (0.035 mmol,
57%), [Bu4N][BF4] (0.030 mmol, 49%)} and after 60 min
1
2J(B, F1) = 17, J(B, F) = 40 Hz]. 19F NMR (CH2Cl2 + CD2Cl2): δ =
4
3
2
–60.1 [qdd J(F2A, BF3) = 6, J(F2A, F1) = 13, J(F2A, F2B) = 167 Hz,
1F, F2A], –61.5 [qdd J(F2B, BF3) = 6, J(F2A, F1) = 12, J(F2B, F2A
)
4
3
2
= 167 Hz, 1F, F2B], –143.2 (m, 1F, F1), –150.9 [dtq (1:1:1:1), J(BF3,
3
F1) = 6, J(BF3, F2) = 6, J(F, B) = 40 Hz, 3F, BF3].
4
1
Reaction of [Bu4N][CF3CϵCBF3]: A.
A
solution of
{[Bu4N][CF3CϵCBF3]
(0.160 mmol)
(44%
conversion),
[Bu4N][CF3CϵCBF3] (0.39 mmol) in CH2Cl2 (3 mL) in a glass am-
poule with a magnetic stir bar was cooled to 0 °C (ice bath) in an
atmosphere of dry argon. Chlorine (1.0 mmol) in dry argon was
bubbled into the stirred solution for 10 min. The ampoule was sealed
and kept at ≈20 °C for 24 h. The solution contained
[Bu4N][CF3CϵCBF3] (0.15 mmol, 62% conversion), [Bu4N][cis-
CF3CCl=CClBF3] (0.06 mmol, 25%), [Bu4N][trans-CF3CCl=CClBF3]
(0.07 mmol, 29%), [Bu4N][CF3CCl2–CCl2BF3] (0.01 mmol, 4%), and
[Bu4N][BF4] (0.10 mmol, 42%) besides traces of CF3CϵCCl [δ(F)
–50.0 (s)], CF3CCl2–CCl3,[29] and minor amounts of unknown prod-
ucts.
[Bu4N][C3F7BF3] (0.067 mmol, 52%), [Bu4N][BF4] (0.060 mmol,
47%)}. In addition, the signals of CF3CH2CF2CH2F (trace quantities
of fluorination of PFB) and HF were detected (19F NMR, 0 °C).
Reactions of Perfluoroalkenyl- and
Perfluoroalkynyltrifluoroborates with Chlorine in
Halocarbon Solutions
Reaction of [Bu4N][trans-C4F9CF=CFBF3]:
A
solution of
[Bu4N][trans-C4F9CF=CFBF3] (0.39 mmol) in CH2Cl2 in a glass am-
poule (3 mL) with a magnetic stir bar was cooled to 0 °C (ice bath) in
an atmosphere of dry argon. Chlorine (0.8 mmol) in dry argon was
slowly bubbled into the stirred solution within 20 min. The ampoule
was sealed and the yellow-greenish solution was stirred for 24 h at
≈20 °C. The 19F NMR spectrum showed the absence of [trans-
C4F9CF=CFBF3]– and new signals of [C4F9CFCl–CFClBF3]–
(0.39 mmol) (C6F6, internal integral standard). After evaporation of the
volatile components at reduced pressure and ≈20 °C, a colorless vis-
cous oil (243 mg, 94%) was obtained.
B. A solution of [Bu4N][CF3CϵCBF3] (0.39 mmol) and chlorine
(0.8 mmol) in CH2Cl2 (3 mL) was prepared as above and stirred at
≈20 °C for 3 h in a test tube closed with a stopper. A probe showed
the presence of [CF3CϵCBF3]– (0.27 mmol, 31% conversion), [cis-
CF3CCl=CClBF3]– (0.07 mmol, 18%), [trans-CF3CCl=CClBF3]–
(0.02 mmol, 5%), [CF3CCl2–CCl2BF3]– (0.01 mmol, 3%), and [BF4]–
(0.02 mmol, 5%). This solution was filled into a glass ampoule, treated
again with chlorine (0.8 mmol) at 0 °C. The ampoule was sealed and
kept at ≈20 °C. After 21 h the yellow-greenish solution contained
[Bu4N][C4F9CFCl–CFClBF3]: 11B NMR (CD3CN): δ = 0.2 [dq 2J(B, [Bu4N][CF3CϵCBF3] (0.15 mmol, 62% conversion), [Bu4N][cis-
F1) = 17, J(B, F) = 40 Hz] (diastereomer C); 0.0 [dq J(B, F1) = 18, CF3CCl=CClBF3] (0.07 mmol, 18%), [Bu4N][trans-CF3CCl=CClBF3]
1
2
1J(B, F) = 38 Hz] (diastereomer A); –0.5 [dq J(B, F1) = 20, J(B, F) (0.07 mmol, 18%), [Bu4N][CF3CCl2CCl2BF3] (0.01 mmol, 3%), and
2
1
= 41 Hz] (diastereomer B) (ratio A:B:C = 59:29:12). 19F NMR [Bu4N][BF4] (0.09 mmol, 23%). The treatment with chlorine
(CD3CN): δ = –79.9 [tt, 4J(F6, F5) = 3, 3J(F6, F4) = 10 Hz, 3F, F6],
(1.0 mmol) was repeated in an ampoule at ≈20 °C for additional 33 h.
–112.2 [md J(F3A, F3B) = 286 Hz, 1F, F3A], –113.2 [md J(F3B, F3A
)
The 19F NMR spectrum confirmed the complete conversion of
2
2
= 286 Hz, 1F, F3B], –118.0 [md 2J(F4A, F4B) = 296 Hz, 1F, F4A], –119.0 [Bu4N][CF3CϵCBF3]. [Bu4N][cis-CF3CCl=CClBF3] (Ͻ0.01 mmol,
[md 2J(F4B, F4A) = 296 Hz, 1F, F4B], –124.4 [md 2J(F5A, F5B) = Ͻ3%),
[Bu4N][trans-CF3CCl=CClBF3]
(0.23 mmol,
59%),
Z. Anorg. Allg. Chem. 2012, 565–579
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.zaac.wiley-vch.de
573

V. V. Bardin, N. Y. Adonin, H.-J. Frohn
ARTICLE
[Bu4N][CF3CCl2–CCl2BF3] (0.03 mmol, 8%), and [Bu4N][BF4]
(0.10 mmol, 26%) were observed besides unknown products.
signals of [C4F9CF=CFBF3]– (0.33 mmol, 75%) (cis/trans = 24:76),
trans-C4F9CF=CFBr[31] (0.11 mmol, 25%), and [BF4]– (0.10 mmol,
23%), besides minor unknown admixtures.
1
[Bu4N][cis-CF3CCl=CClBF3]: 11B NMR (CD3CN): δ = 0.0 [q, J(B,
F) = 37 Hz, BF3]. 19F NMR (CD3CN): δ = –59.2 [q, 5J(F3, BF) = Reactions of [Bu4N][(cis and trans)-CnF2n+1CF=CFBF3]: A. A solu-
10 Hz, 3F, F3], –138.5 [qq (1:1:1:1), 5J(FB, F3) = 10, 1J(F, B) = 37 Hz, tion of [Bu4N][C2F5CF=CFBF3] (0.15 mmol) (cis/trans = 60:40), and
5
3F, BF3]. 19F NMR (CH2Cl2): δ = –60.5 [q, J(F3, BF) = 10 Hz, 3F, bromine (0.27 mmol) in CH2Cl2 (1 mL) was heated at 65–70 °C for 9
5
1
F3], –139.2 [qq (1:1:1:1), J(FB, F3) = 9, J(F, B) = 38 Hz, 3F, BF3].
h and left overnight at ≈20 °C. The yellow solution was washed with
cold water and dried with MgSO4. The 19F NMR spectrum showed
the resonances of [C2F5CF=CFBF3]– (0.08 mmol, 53%) (cis/trans =
75:25), C2F5CF=CFBr (0.07 mmol, 46%) (cis/trans = 37:63), and
[BF4]– (0.07 mmol, 46%).
[Bu4N][trans-CF3CCl=CClBF3]: 11B NMR (CD3CN): δ = 0.7 [q,
5
1J(B, F) = 36 Hz, BF3]. 19F NMR (CD3CN): δ = –68.7 [q, J(F3, BF)
= 8 Hz, 3F, F3], –145.4 [qq (1:1:1:1), 5J(FB, F3) = 8, 1J(F, B) = 35 Hz,
3F, BF3]. 19F NMR (CH2Cl2): δ = –70.1 [q, 5J(F3, BF) = 8 Hz, 3F,
5
1
F3], –146.3 [qq (1:1:1:1), J(FB, F3) = 7, J(F, B) = 36 Hz, 3F, BF3].
B. A solution of [Bu4N][C4F9CF=CFBF3]– (0.19 mmol) (cis/trans =
42:58), and bromine (0.27 mmol) in CH2Cl2 (1 mL) was heated at 65–
70 °C for 11 h and left overnight at ≈20 °C. The resulting yellow solu-
tion was washed with cold water and dried with MgSO4. The 19F NMR
spectrum displayed the resonances of [Bu4N][C4F9CF=CFBF3]–
(0.06 mmol, 32%) (cis/trans = 67:33), C4F9CF=CFBr (0.13 mmol,
68%) (cis/trans = 15:85), and [BF4]– (0.18 mmol, 95%).
[Bu4N][CF3CCl2–CCl2BF3]: 11B NMR (CD3CN): δ = 0.1 [q, 1J(B,
F) = 39 Hz, BF3] (conformer A); –2.0 [q, 1J(B, F) = 44 Hz, BF3]
(conformer B); 0.1 [q, 1J(B, F) = 36 Hz, BF3] (conformer C) (ratio
A:B:C = 56:16:28]. 19F NMR (CD3CN): δ = –59.4 (s, 3F, F3), –140.9
1
[q (1:1:1:1), J(F, B) = 38 Hz, 3F, BF3] (conformer A); –60.0 (s, 3F,
F3),–141.8 [q (1:1:1:1), 1J(F, B) = 44 Hz, 3F, BF3] (conformer B);
–60.0 (s, 3F, F3), –135.1 [q (1:1:1:1), 1J(F, B) = 35 Hz, 3F, BF3] (con-
former C) (ratio A:B:C = 43:24:33).
3
cis-C4F9CF=CFBr: 19F NMR (CH2Cl2): δ = –83.2 [dt, J(F1, F2) =
4
4
3
16, J(F1, F3) = 4 Hz, 1F, F1], –115.6 [td, J(F3, F5) = 10, J(F3, F2) =
12 Hz, 2F, F3], –140.5 (m, 1F, F2); the resonances of the fluorine atoms
F4,5,6 overlapped with those of trans-C4F9CF = CFBr.
Reactions of Organyltrifluoroborates with Bromine in
Halocarbon Solutions
Reaction of [Bu4N][CF2=CFBF3]: A solution of bromine (42 mg,
0.26 mmol) in CH2Cl2 (0.2 mL) was added dropwise to a stirred solu-
tion of [Bu4N][CF2=CFBF3] (86 mg, 0.22 mmol) in CH2Cl2 (0.5 mL)
at 0–2 °C. After 15 min, the 11B and 19F NMR spectra of the pale
yellow solution showed the absence of [CF2=CFBF3]– and the forma-
tion of the molecule CF2=CFBr (0.10 mmol, 45%), of the anions
[CF2Br–CFBrBF3]– (0.04 mmol, 18%) and [BF4]– (0.12 mmol, 55%)
besides traces of CF2=CFH and CF2Br–CFBr2.
Reaction of [Bu4N][cis-C2F5CF=CFBF3]: A solution of bromine
(51 mg, 0.32 mmol) in CH2Cl2 (1.2 mL) was added dropwise to a
stirred solution of [Bu4N][cis-C2F5CF=CFBF3] (152 mg, 0.31 mmol)
in CH2Cl2 (1 mL) at ≈20 °C. After stirring for 21 h the orange-red
solution contained [Bu4N][C2F5CF=CFBF3] (0.25 mmol, 81%)
(cis/trans = 72:28), C2F5CF=CFBr[30] (0.04 mmol, 13%) (cis/trans =
25:75), C2F5CFBr–CFHBr (0.02 mmol, 6%), and [Bu4N][BF4]
(0.05 mmol, 16%]. After 48 h, the 19F NMR spectrum of the pale
yellow solution showed the resonances of [Bu4N][C2F5CF=CFBF3] [dq J(B, F1) = 16, J(B, F) = 40 Hz]. 19F NMR (CH2Cl2 + CD2Cl2):
(0.15 mmol, 48%) (cis/trans = 60:40), C2F5CF=CFBr (0.05 mmol,
16%) (cis/trans = 20:80), cis-C2F5CF=CFH[24] (0.01 mmol, 3%), = 22, 2J(F2B, F2A) = 165 Hz, 1F, F2B], –138.0 (m, 1F, F1), –147.8 (BF3,
[Bu4N][CF2Br–CFBrBF3]: 11B NMR (CH2Cl2 + CD2Cl2): δ = –0.8
2
1
2
3
δ = –50.4 [d, J(F2A, F2B) = 165 Hz, 1F, F2A], –52.3 [dd, J(F2A, F1)
C2F5CFBr–CFHBr[30] [δ(F) –85.5 (m, 3F, F4), –119.9 (m, 2F, F3),
–132.1 (m, 1F, F2), –148.6 (d, 2J(F1, H1) = 52 Hz, 1F, F1)] (0.01 mmol,
3%), and [Bu4N][BF4] (0.06 mmol, 19%). To support the identifica-
tion of C2F5CFBr–CFHBr in the reaction solution by NMR spec-
overlapping with the signal of the other conformers) (conformer A); δ
= –48.0 [qd, 4J(F2A, BF3) = 17, 2J(F2A, F2B) = 161 Hz, 1F, F2A], –52.1
[qdd 4J(F2B, BF3) = 8, 3J(F2B, F1) = 27, 2J(F2B, F2A) = 161 Hz, 1F,
F2B], –134.0 (m, 1F, F1), –147.8 (BF3, overlapping with the signal of
4
troscopy, the homologue C4F9CFBr–CFHBr was prepared and charac- the other conformers) (conformer B); δ = –48.3 [qdd J(F2A, BF3) =
terized (cf. last experiment).
9, 3J(F2A, F1) = 10, 2J(F2A, F2B) = 167 Hz, 1F, F2A], –52.2 [qdd 4J(F2B
,
BF3) = 8, 3J(F2B, F1) = 15, 2J(F2B, F2A) = 167 Hz, 1F, F2B], –134.0
(m, 1F, F1), –147.8 (BF3, overlapping with the signal of the other
conformers) (conformer C) (ratio A:B:C = 53:25:22).
Reaction of [Bu4N][trans-C4F9CF=CFBF3]: A. A solution of bro-
mine (48 mg, 0.30 mmol) in CH2Cl2 (1.1 mL) was added dropwise to
a solution of [Bu4N][trans-C4F9CF=CFBF3] (224 mg, 0.38 mmol) in
CH2Cl2 (3 mL) at ≈20 °C. The red solution was stirred without protec-
Reaction of [Bu4N][trans-C4H9CF=CFBF3]: A. A solution of bro-
tion against light. After 24 h the solution was still red colored. After mine (0.30 mmol) in CHCl3 (1 mL) was added dropwise to a solution
66 h, the 19F NMR spectrum of the now pale yellow solution showed of [Bu4N][trans-C4H9CF=CFBF3] (0.30 mmol) in CHCl3 (1 mL) at
the resonances of [C4F9CF=CFBF3]– (0.29 mmol, 76%) (cis/trans = 0 °C within 15 min. The color of bromine disappeared immediately
62:38), C4F9CF=CFBr (0.06 mmol, 16%) (cis/trans = 17:83), and
[BF4]– (0.04 mmol, 11%). Further maintain at ≈20 °C for 28 h did not
change the composition of the reaction solution.
after addition. The yellow solution was stirred for 1 h at ≈20 °C and
diluted with CDCl3. The 1H and 19F NMR spectra showed the reso-
nances of trans-C4H9CF=CFBr (0.17 mmol, 57%), trans-
C4H9CF=CFH[32] (0.10 mmol, 33%), and [Bu4N][BF4] (0.33 mmol,
110%) besides a trace of C4H9CFBr–CFHBr.
B. A solution of bromine (99 mg, 0.62 mmol) and [Bu4N][trans-
C4F9CF=CFBF3] (259 mg, 0.44 mmol) in CH2Cl2 (5.5 mL) was stirred
at ≈20 °C in a flask coated with aluminum foil. After 24 h the 19F The solution was treated with a further equivalent of bromine
NMR spectrum of the red solution displayed the signals of
[C4F9CF=CFBF3]– (0.35 mmol, 80%) (cis/trans = 17:83), trans-
C4F9CF=CFBr (0.08 mmol, 18%), and [BF4]– (0.08 mmol, 18%). Af-
ter 84 h the 19F NMR spectrum of the still red solution showed the
(0.30 mmol) in CHCl3 (1 mL) and stirred at ≈20 °C for 15 h. All vola-
tiles were distilled off at 80 °C (bath). The residue was cooled to
≈20 °C and extracted with CCl4 (2ϫ1 mL). The extract was passed
through a short column (2 cm length) with anhydrous MgSO4 and a
574
www.zaac.wiley-vch.de
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2012, 565–579

1,2-Addition of Halogen and/or Replacement of Boron by Halogen
1
probe was diluted with CDCl3. The H and 19F NMR spectra showed (total 196 mg, 1.22 mmol) in CH2Cl2 (0.8 mL) was added. After stir-
the resonances of trans-C4H9CF=CFBr, cis-C4H9CF=CFBr,
C4H9CFBr–CFBr2, and C4H9CFBr–CFHBr (molar ratio = 11:7:35:47),
besides minor amounts of unknown products.
ring at ≈20 °C for 24 h, the red solution contained [Bu4N][BF4]
(0.43 mmol, 75%), CF3CBr=CBr2 (0.43 mmol, 75%), and
[Bu4N][CF3CBr=CBrBF3] (0.09 mmol, 16%) (cis/trans = 62:38), (19F
NMR). The solution was concentrated on an evaporator and the oil
was extracted with CCl4 (0.5 mL). The pale yellow extract contained
CF3CBr=CBr2 (0.40 mmol, 70%) (13C, 19F NMR).
B. A solution of bromine (0.21 mmol) in CH2Cl2 (0.7 mL) was added
dropwise to a solution of [Bu4N][trans-C4H9CF=CFBF3] (0.21 mmol)
in CH2Cl2 (2.5 mL) at ≈20 °C within 5 min. The color of bromine
disappeared immediately after addition. The 19F NMR spectrum
showed the resonances of trans-C4H9CF=CFBr (0.15 mmol, 71%),
trans-C4H9CF=CFH (0.05 mmol, 24%), and [Bu4N][BF4] (0.21 mmol,
100%).
1
[Bu4N][CF3CBr=CBrBF3]: 11B NMR (CH2Cl2): δ = 0.3 [q, J(B, F)
= 38 Hz, BF3]. 19F NMR (CH2Cl2): δ = –57.4 [q, 5J(F3, BF3) = 11 Hz,
1
5
3F, F3], –137.5 [q (1:1:1:1)q, J(F, B) = 37, J(BF3, F3) = 11 Hz, 3F,
BF3] ([cis-CF3CBr=CBrBF3]–); –57.8 [q, J(F3, BF3) = 1 Hz, 3F, F3],
–140.4 [q (1:1:1:1), 1J(F, B)
5
= 38 Hz, 3F, BF3] ([trans-
trans-C4H9CF=CFBr: 1H NMR (CDCl3 + CCl4): δ = 2.41 [tdd,
CF3CBr=CBrBF3]–).
4
3J(H3, H4) = 7, J(H3, F1) = 6, 3J(H3, F2) = 21 Hz, 2 H, H3], 1.54 (m,
CF3CBr=CBr2: 13C NMR (CCl4): δ = 121.0 [q, 1J(C-3, F3) = 275 Hz,
3
CH2), 1.37 (m, CH2), 0.93 [t, J(H6, H5) = 7 Hz, 3 H, H6]. 19F NMR
2
3
C-3], 115.8 [q, J(C-2, F3) = 39 Hz, C-2], 99.9 [q, J(C-1, F3) = 3 Hz,
4
3
(CDCl3 + CCl4): δ = –127.3 [td, J(F1, H3) = 5, J(F1, F2) = 134 Hz,
C-1]. 19F NMR (CCl4): δ = –58.6 (s, 3F, F3).
1F, F1], –140.0 [td, J(F2, H3) = 22, J(F2, F1) = 134 Hz, 1F, F2].
3
3
Reaction of [Bu4N][C4H9CϵCBF3]:
A solution of bromine
1
cis-C4H9CF=CFBr: H NMR (CDCl3 + CCl4): δ = 2.50 [td, 3J(H3,
(0.30 mmol) in CHCl3 (1 mL) was added dropwise to a solution of
[Bu4N][C4H9CϵCBF3] (0.28 mmol) in CHCl3 (1 mL) at 0 °C within
15 min. The color of bromine disappeared immediately after addition.
The yellow solution was stirred for 1 h at ≈20 °C. The 1H and 19F
NMR spectra showed the resonances of C4H9CϵCBr[36] (0.08 mmol,
H4) = 7, 3J(H3, F2) = 21 Hz, 2 H, H3], 1.5–1.3 (m, 2CH2), 0.9 [t, 3J(H6,
H5) = 7 Hz, 3 H, H6]. 19F NMR (CDCl3 + CCl4): δ = –108.7 [d, 3J(F1,
F2) = 14 Hz, 1F, F1], –128.4 [td, J(F2, H3) = 22, J(F2, F1) = 14 Hz,
3
3
1F, F2].
29%), C4H9CϵCH (0.07 mmol, 25%), trans-C4H9CBr=CHBr[36]
1
3
C4H9CFBr–CFHBr: H NMR (CDCl3 + CCl4): δ = 6.57 [dd, J(H1,
[36]
F2) = 5, J(H1, F1) = 48 Hz, 1 H, H1], 2.2 (m, 2H3), 1.5–1.3 (m, 4H,
2
(0.05 mmol, 18%), C4H9CBr=CBr2
(0.05 mmol, 18%), and
H4,5), 0.91 [t, 3J(H6, H5) = 7 Hz, 3H, H6] {cf. C7H15CFBrCFHBr
[Bu4N][BF4] (0.28 mmol, 100%).
(CDCl3): δ = 6.6 [dd, J(H1, F2) = 5, J(H1, F1) = 48.1 Hz, 1 H, H1]
3
2
To confirm the presence of the alkynes C4H9CϵCH and C4H9CϵCBr,
the solution was treated with bromine (0.33 mmol) in CHCl3 (1 mL)
and stirred at ≈20 °C for 15 h. All volatiles were distilled off at 80 °C
(bath), the residue was cooled to ≈20 °C and extracted with CCl4
(2ϫ1 mL). The extract was passed through a short column (2 cm
length) with anhydrous MgSO4 and a probe was diluted with CDCl3.
The 1H and 19F NMR spectra showed the resonances of trans-
C4H9CBr=CHBr, cis-C4H9CBr=CHBr,[36] and C4H9CBr=CBr2 (molar
ratio = 40:16:44) besides minor amounts of unknown products and the
absence of the alkynes and of [Bu4N][BF4].
(diastereomer A); 6.5 [dd, J(H1, F2) = 10, J(H1, F1) = 48.1 Hz, 1 H,
3
2
H1] (diastereomer B); the signals of the C7H15 moiety were not
given[33]}. 19F NMR (CDCl3 + CCl4): δ = –113.1 [dddd, J(F2, H1) =
3
4, 3J(F2, F1) = 32, 3J(F2, H3A) = 8, 3J(F2, H3B) = 28 Hz, 1F, F2], –143.8
[dd, 3J(F1, F2)
= =
32, 2J(F1, H1) 48 Hz, 1F, F1]. {cf.
C7H15CFBrCFHBr (CDCl3): δ = –112.6 [d, J(F2, F1) = 31.3 Hz, 1F,
3
F2], –142.9 [dd, J(F1, F2) = 31.3, J(F1, H1) = 48.1 Hz, 1F, F1] (dia-
3
2
stereomer A); δ –115.7 [d, J(F2, F1) = 24.4 Hz, 1F, F2], –142.1 [dd,
3
3J(F1, F2) = 24.4, J(F1, H1) = 48.1 Hz, 1F, F1] (diastereomer B)[33]}.
2
C4H9CFBr–CFBr2: 19F NMR (CDCl3 + CCl4): δ –62.8 [d, 3J(F1, F2)
Reaction of [Bu4N][C4H9BF3]: A solution of bromine (0.30 mmol) in
CHCl3 (1 mL) was added dropwise to a solution of [Bu4N][C4H9BF3]
(0.30 mmol) in CHCl3 (1 mL) at 0 °C within 15 min. The color of
bromine disappeared immediately after addition. The yellow solution
3
= 22 Hz, 1F, F1], –110.5 [dd, J(F2, F1) = 25, 3J(F2, H3A) = 35 Hz, 1F,
F2] {cf. C7H15CFBrCFBr2 (CDCl3): δ = –62.1 [d, 3J(F1, F2) = 25.9 Hz,
3
3
1F, F1], –109.7 [dd, J(F2, F1) = 25.9, J(F2, H3A) = 38.2 Hz, 1F, F2)
[33]}.
1
was stirred for 1 h at ≈20 °C. The H and 19F NMR spectra showed
the resonances of C4H9Br (0.15 mmol, 50%), C4H10 (0.13 mmol,
43%), and [Bu4N][BF4] (0.28 mmol, 93%).
Reaction of [Bu4N][C4H9CH=CHBF3]: A solution of bromine
(0.33 mmol) in CHCl3 (1 mL) was added dropwise to a solution of
[Bu4N][C4H9CH=CHBF3] (0.33 mmol) (cis{trans = 67:33) in CHCl3
(1 mL) at ≈20 °C within 10 min. The color of bromine disappeared
immediately after addition. The yellow solution was stirred for 1 h.
The 1H and 19F NMR spectra displayed the resonances of
Attempted Reaction of [Bu4N][C6F13BF3] with Bromine: A solution
of [Bu4N][C6F13BF3] (0.30 mmol) in CHCl3 (2.3 mL) and bromine
(0.30 mmol) in CHCl3 (1 mL) was stirred at ≈20 °C for 3 d. No reac-
tion was detected (19F NMR).
C4H9CH=CHBr[34] (0.16 mmol, 48%) (cis{trans
=
63:37),
C4H9CHBr–CH2Br[35] (0.10 mmol, 30%), and [Bu4N][BF4]
(0.33 mmol, 100%).
Reactions of Fluoroalkenyl- and
Fluoroalkynyltrifluoroborates with Bromine Trifluoride-
Bromine (1:1, Equivalent of “BrF”)
Reaction of [Bu4N][CF3CϵCBF3]: Bromine (89 mg, 0.55 mmol) dis-
solved in CH2Cl2 (0.5 mL) was added to a stirred cold (0 °C) solution
of [Bu4N][CF3CϵCBF3] (230 mg, 0.57 mmol) in CH2Cl2 (1.5 mL). Preparation of Bromine Trifluoride-bromine (1:1) Solutions: A
After 10 min the bath was removed and the solution was stirred at
solution of BrF3 (100 mg, 0.73 mmol) in PFB (0.4 mL) was stirred
with dried NaF (32 mg) for 2 h and centrifuged. The mother liquor
was transferred into a 8 mm. i. d. FEP trap equipped with a magnetic
≈20 °C over a period of 1 h. The 11B and 19F NMR spectra showed
the formation of [Bu4N][CF3CBr=CBrBF3] (cis/trans
= 62:38)
(0.45 mmol, 92%), [Bu4N][BF4], and CF3CBr=CBr2 (both stir bar in an atmosphere of dry argon. A solution of bromine (116 mg,
~0.03 mmol, 6%]. The conversion of the starting borate was deter- 0.73 mmol) in PFB (0.5 mL) was added in one portion. A red-brown
mined to 86%. A second portion of bromine (107 mg, 0.66 mmol) solution resulted which was diluted with PFB (0.1 mL).
Z. Anorg. Allg. Chem. 2012, 565–579
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
575

V. V. Bardin, N. Y. Adonin, H.-J. Frohn
ARTICLE
(BrF3–Br2) (1:1): 19F NMR (PFB 24 °C): δ = –23.0 (s, Δν1/2
=
[Bu4N][CF3CBr2–CF2BF3] (70 μmol, 28%), [Bu4N][BF4] (138 μmol,
1512 Hz) {cf. with 19F NMR spectrum of BrF3 in PFB at 24 °C: δ = 55%), and CF3CBr=CBr2 (80 μmol, 32%) (19F NMR). The solvent
–17.9 (s, Δν1/2 = 27 Hz)[4]}.
was removed on an evaporator at Ͻ30 °C (bath) and the remaining
yellow oil was extracted with CCl4 (1 mL). The extract contained
CF3CBr=CBr2 besides residual PFB (19F NMR). In all cases, signals
of minor unrecognized components were observed besides PFB. In
the first step, the presence of [Bu4N][CF3CBr2–CFBrBF3] (Յ5 μmol)
The solubility of bromine in PFB (160 mg, 1.00 mmol per mL of PFB;
21 °C) was determined visually by portion-wise addition of PFP to Br2
in a narrow-diameter tube.
4
5
{signals at δ = –57.7 [dq J(F3, F1) = 9, J(F3, BF3) = 9 Hz, 3F, F3),
Reaction of [Bu4N][cis-C2F5CF=CFBF3] with “BrF”: A solution of
BrF3 (0.10 mmol) and Br2 (0.10 mmol) (0.30 mmol “BrF”) in PFB
–68.0 (m, 1F, F1), –139.7 [q, J(F,B) = 38 Hz, 3F, BF3} was assumed.
1
(0.1 mL) was added to
C2F5CF=CFBF3] (0.63 mmol) in PFB (2 mL). The red-orange solution
was stirred at ≈20 °C for 5 h and changed the color to yellow. The 19
NMR spectrum showed the resonances of [Bu4N][C2F5CF=CFBF3]
(0.45 mmol, 71%) (cis/trans = 56:44), [Bu4N][C2F5CFBr–CF2BF3]
(0.16 mmol, 25%) besides C2F5CF=CFBr (0.02 mmol, 3%) (cis/trans
= 40:60) and [Bu4N][BF4] (0.02 mmol, 3%). No changes were ob-
served after further 50 h at ≈20 °C.
a
stirred solution of [Bu4N][cis-
Reactions of Tetrabutylammonium Organyltrifluoroborates
with Iodine Chloride in Halocarbon Solutions
F
Reaction of [Bu4N][trans-C4F9CF=CFBF3]:
A
solution of
[Bu4N][trans-C4F9CF=CFBF3] (190 mg, 0.32 mmol) in CH2Cl2
(0.5 mL) was treated with portions of a solution of ICl (67 mg,
0.41 mmol) in CH2Cl2 (0.3 mL) at ≈20 °C. The addition of the first
portion of ICl (0.12 mmol, 0.38 equiv.) ended with a molar ratio of
[Bu4N][trans-C4F9CF=CFBF3] to trans-C4F9CF=CFI of 64:36 which
did not change within 20 h. The addition of following portions of
ICl and sequential NMR measurements after 30 min showed the fast
conversion of [Bu4N][trans-C4F9CF=CFBF3] to trans-C4F9CF=CFI
(n equiv. ICl/ratio ([Bu4N][trans-C4F9CF=CFBF3]:trans-C4F9CF=CFI):
0.38/56:44; 0.53/32:68; 1.28/0:100). The 19F NMR spectra contained
a broadened signal (Δν1/2 = 255 Hz) of a F-B resonance at δ =
–144 ppm.
Reaction of [Bu4N][CF2=CFBF3] with “BrF”:
A solution of
[Bu4N][CF2=CFBF3] (136 mg, 0.34 mmol) and [Bu4N][PF6] (35 mg,
0.09 mmol) (internal integral standard) in PFB (2.1 mL) in a 11.7 mm.
i. d. PFA trap was cooled to –15 °C. Afterwards, a solution of BrF3
(0.11 mmol) and Br2 (0.11 mmol) (0.33 mmol of “BrF”) in PFB
(0.15 mL) was added in one portion with stirring. Within 1 min a col-
orless solution was formed. After 15 min at –15 °C, the solution con-
tained [Bu4N][BF4] (0.34 mmol, 100%), CF2=CFBr (0.17 mmol,
50%), and CF3–CF2Br (0.11 mmol, 32%) and traces of CF2=CFH and
[Bu4N][CF2=CFBF3] besides the standard [Bu4N][PF6] (11B, 19F
NMR).
3
trans-C4F9CF=CFI: 19F NMR (CH2Cl2): δ = –81.8 [tt, J(F6, F5) =
4
5
4
3, J(F6, F4) = 10 Hz, 3F, F6], –106.9 [ttd, J(F1, F4) = 6, J(F1, F3) =
27, 3J(F1, F2) = 150 Hz, 1F, F1], –117.4 [dtd 3J(F3, F2) = 13, 4J(F3,
F5) = 13, J(F3, F1) = 26 Hz, 2F, F3], –125.2 (m, 2F, F4), –127.1 (m,
4
Reaction of [Bu4N][trans-C4H9CF=CFBF3] with “BrF”: A cold
(0 °C) solution of BrF3 (0.10 mmol) and Br2 (0.10 mmol) (0.30 mmol
“BrF") in PFB (0.1 mL) was added to a cold (0 °C) stirred solution of
[Bu4N][trans-C4H9CF=CFBF3] (0.33 mmol) in PFB (9 mL). The pale-
yellow solution was stirred at 0 °C for 30 min and at ≈20 °C for
30 min. The 19F NMR spectrum showed the resonances of
[Bu4N][trans-C4H9CF=CFBF3] (0.06 mmol, 82% conversion), trans-
C4H9CF=CFBr (0.17 mmol, 63%), and [Bu4N][BF4] (0.24 mmol,
89%). The volatile components were distilled off and collected and
the residue was extracted with CCl4 (2 mL). The extract was combined
2F, F5), –145.9 [md 3J(F2, F1) = 150 Hz, 1F, F2] {ref.[31] 19F NMR
(CH2Cl2): δ = –81.7 (3F, F6), –106.6 [ttd, J(F1, F4) = 5.5, J(F1, F3)
5
4
= 27, 3J(F1, F2) = 151 Hz, 1F, F1], –117.0 (2F, F3), –124.8 (2F, F4),
–126.9 (2F, F5), –144.8 [d, J(F2, F1) = 151 Hz, 1F, F2]}.
3
Reaction of [Bu4N][CF2=C(CF3)BF3]: A solution of ICl (120 mg,
0.73 mmol) in CH2Cl2 (0.5 mL) was added dropwise to a solution of
[Bu4N][CF2=C(CF3)BF3] (273 mg, 0.62 mmol) in CH2Cl2 (0.7 mL) at
≈20 °C over a period of 30 min. The 19F NMR spectrum showed the
formation of CF2=C(CF3)I (0.47 mmol, 76%) and CF2=C(CF2Cl)I
(0.04 mmol, 6%) and contained a broadened F-B signal at δ =
–144 ppm (Δν1/2 = 347 Hz). The 11B NMR spectrum contained unre-
solved signals at 3.5 and 0 ppm in the integral ratio 3:100.
1
with the distillate and concentrated to a volume of 2 mL. The H and
19F NMR spectra showed the presence of trans-C4H9CF=CFBr
(0.24 mmol, 73%), besides an admixture of PFB and traces of cis-
C4H9CF=CFBr, cis- and trans-C4H9CF=CFH.
C4H9CF=CFBr: MS (EI) calcd. for C6H9BrF2 197.9850209 (79Br),
4
CF2=C(CF3)I: 19F NMR (CH2Cl2): δ = –58.6 [dd, J(F3, F1cis) = 11,
found 197.9852 (79Br).
4J(F3, F1trans) = 22 Hz, 3F, F3], –61.7 [dq 2J(F1trans, F1cis) = 3,
4J(F1trans, F3) = 22 Hz, 1F, F1trans], –61.9 [dq 2J(F1cis, F1trans) = 3,
4J(F1cis, F3) = 11 Hz, 1F, F1cis] {ref.[37] 19F NMR (DMF): δ = –58.8
[d 22 Hz, d 11 Hz, 3F, F3], –61.6 [q 22 Hz, d 2 Hz, 1F], –62.0 [q
11 Hz, d 3 Hz, 1F]}.
Reaction of [Bu4N][CF3CϵCBF3] with “BrF”: A solution of
[Bu4N][CF3CϵCBF3] (101 mg, 250 μmol) and [Bu4N][PF6] (59 mg,
153 μmol) (internal integral standard) in PFB (1.3 mL) in a 8.0 mm.
i. d. FEP trap was cooled to ≈0 °C. Afterwards, solutions of BrF3 (100
μmol) and Br2 (100 μmol) (300 μmol of “BrF”) in PFB (0.1 mL) were
added. The solution was stirred at ≈20 °C for 0.5 h till discoloration.
It contained [Bu4N][CF3CϵCBF3] (180 μmol, 28% conversion),
CF2=C(CF2Cl)I: 19F NMR (CH2Cl2): δ = –43.7 [dd, 4J(F3, F1cis) =
9, 4J(F3, F1trans) = 29 Hz, 2F, F3], –61.4 [dt, 2J(F1trans, F1cis) = 4,
4J(F1trans, F3) = 29 Hz, 1F, F1trans], –63.3 [dt, 2J(F1cis, F1trans) = 4,
4J(F1cis, F3) = 9 Hz, 1F, F1cis].
[Bu4N][CF3CBr=CBrBF3] (32 μmol, 46%) (cis/trans
= 63:37),
[Bu4N][CF3CBr2–CFBrBF3] (5 μmol, 7%), [Bu4N][CF3CBr2–CF2BF3]
(14 μmol, 20%), [Bu4N][BF4] (35 μmol, 50%), CF3CϵCBr (6 μmol,
9%), and CF3CBr=CBr2 (12 μmol, 17%) (19F NMR). The solution
Reaction of [Bu4N][CF2=CFBF3]: A dark solution of ICl (66 mg,
0.40 mmol) in CH2Cl2 (0.3 mL) was added dropwise to a stirred solu-
was reacted with further BrF3 (300 μmol) and Br2 (300 μmol) (total tion of [Bu4N][CF2=CFBF3] (110 mg, 0.28 mmol) in CH2Cl2 (0.5 mL)
amount: 1200 μmol of “BrF”) in PFB (0.1 mL). The red-orange solu- at ≈20 °C. The yellowish solution was stirred for 15 min. The 19F
tion was stirred at ≈20 °C for 4 h and became pale yellow. It contained NMR spectrum displayed the formation of CF2=CFI (0.21 mmol,
[Bu4N][CF3CBr=CBrBF3] (21 μmol, 8%) (cis/trans
=
86:14),
75%) and contained a broadened F-B signal at δ = –144 ppm (Δν1/2
576 www.zaac.wiley-vch.de
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2012, 565–579

1,2-Addition of Halogen and/or Replacement of Boron by Halogen
= 268 Hz). The 11B NMR spectrum contained unresolved signals at (2 mL) at ≈20 °C for 0.5 h. The separated mother liquor showed the
2.5 and –1.0 ppm in the ratio 1:100 and no resonances of either
presence of CF2Cl–CFCl2 (0.01 mmol, 1%) (19F NMR). The solid part
was dried in vacuo, extracted with MeCN (2 mL). The extract was
evaporated to dryness to yield a white solid, K[CF2Cl–CFClBF3],
(155 mg, 65%).
[CF2=CFBF3]– nor [CF2X–CFYBF3]–.
Reaction of [Bu4N][trans-C4H9CF=CFBF3]: A solution of ICl
(0.38 mmol) in CHCl3 (1 mL) was added dropwise to a solution of
[Bu4N][trans-C4H9CF=CFBF3] (0.36 mmol) in CHCl3 (1.1 mL) at
≈20 °C within 5 min. The color of ICl disappeared immediately after
dropping. The yellow solution was stirred for 0.5 h at ≈20 °C and
diluted with CDCl3. The 1H and 19F NMR spectra showed the reso-
nances of trans-C4H9CF=CFI (0.23 mmol, 64%), trans-C4H9CF=CFH
(0.13 mmol, 36%), and [Bu4N][BF4] (0.36 mmol, 100%; a singlet at
When a stirred suspension of K[CF2Cl–CFClBF3] (155 mg) in dichlo-
romethane (2 mL) was treated with further chlorine (4.5 mmol)
(≈20 °C, 30 min), no further reaction occurred. The 19F NMR spectrum
of the mother liquor showed no fluoroorganic compounds. After evap-
oration of the suspension in vacuo to dryness, K[CF2Cl–CFClBF3]
(145 mg) was recovered.
δ = –152.2 ppm) besides a weak resonance at δ = –126 ppm (Δν1/2
=
2
K[CF2Cl–CFClBF3]: 11B NMR (CH3CN): δ = –0.1 [dq J(B, F1) =
97 Hz).
16, 1J(B, F) = 39 Hz]. 19F NMR (CH3CN): δ = –60.2 [qdd 4J(F2A
,
trans-C4H9CF=CFI: 1H NMR (CDCl3 + CHCl3): δ = 2.46 [tdd,
BF3) = 7, 3J(F2A, F1) = 13, 2J(F2A, F2B) = 169 Hz, 1F, F2A], –61.5
[qdd 4J(F2B, BF3) = 6, 3J(F2B, F1) = 12, 2J(F2B, F2A) = 169 Hz, 1F,
F2B], –142.0 (m, 1F, F1), –149.5 [dtq (1:1:1:1), 3J(BF3, F1) = 6, 4J(BF3,
F2) = 6, 1J(F, B) = 39 Hz, 3F, BF3]. Anal. for C2BCl2F6K (258,83):
calcd. C 9.28; Cl 27.40%; F 44.04; found: C 9.1; Cl 27.2; F 44.5%.
3J(H3, H4) = 7, J(H3, F1) = 6, J(H3, F2) = 21 Hz, 2H, H3], 1.6–1.3
4
3
(m, 4H, H4, 5), 0.87 [t, J(H6, H5) = 7 Hz, 3H, H6] {ref.[38] δ = 2.65
3
3
4
[dq J(H3, F2) = 20, J(H3, F1) = 7.5 Hz, 2H, H3], 1.5 (4H), 0.95 (t,
3H, H6)}. 19F NMR (CDCl3 + CHCl3): δ = –129.1 [td, J(F1, H3) =
4
3
3
3
6, J(F1, F2) = 141 Hz, 1F, F1], –130.9 [td, J(F2, H3) = 22, J(F2, F1)
= 141 Hz, 1F, F2] {ref.[38] δ = –128.2 (dt, 1F, F1), –130.6 (dt, 1F, F2);
3J(F1, F2) = 141 Hz}.
Attempted Reaction of K[trans-C4F9CF=CFBF3]: Chlorine
(3 mmol) in argon was slowly bubbled into a stirred suspension of
K[trans-C4F9CF=CFBF3] (249 mg, 0.64 mmol) in 1,2-dichloroethane
(2.5 mL) for 1 h. The solid was filtered off. After drying on air 222 mg
of the starting borate was recovered (19F NMR).
Reaction of [Bu4N][C4H9CH=CHBF3]:
(0.27 mmol) in CH2Cl2 (0.9 mL) was added dropwise within 5 min to
solution of [Bu4N][C4H9CH=CHBF3] (cis/trans 67:33)
A
solution of ICl
a
=
(0.27 mmol) in CH2Cl2 (1 mL) at 20 °C. The color of ICl disappeared
immediately after dropping. After the last drop a red-brownish solution
1
Reactions on the Surface of Potassium
Organyltrifluoroborates with Bromine in Halocarbons
remained which was stirred for 1 h at 20 °C. The H NMR spectrum
showed the resonances of C4H9CH=CHI[39] (0.11 mmol, 41%)
(cis/trans
=
55:45), C4H9CHCl–CH2I[40] (0.03 mmol, 11%),
Reaction of K[CF2=CFBF3]: A. Bromine (95 mg, 0.59 mmol) was
added to a suspension of K[CF2=CFBF3] (110 mg, 0.55 mmol) in
CH2Cl2 (1 mL) at ≈0 °C. The suspension was stirred for 1 h before the
mother liquor was separated. The precipitate was washed with CH2Cl2
(2ϫ2 mL). The combined extracts contained CF2Br–CFBr2
(0.03 mmol, 5%) (19F NMR). The solid residue was dried in vacuo and
extracted with MeCN. The extract was evaporated to dryness yielding
K[CF2Br–CFBrBF3] (178 mg, 93% yield).
C4H9CHCl–CH2Cl[41] (0.03 mmol, 11%), and [Bu4N][BF4]
(0.27 mmol, 100%). To remove the latter salt, the solution was diluted
with CCl4 (2 mL), and the volatile components were distilled off at
70 °C (bath). The yellow distillate contained drops of a dense red oil,
which were removed by passing through a short column (length
1.5 cm) filled with anhydrous MgSO4. The yellow liquid phase con-
tained C4H9CH=CHI[39] (31%) (cis/trans = 58:42), C4H9CHCl–CH2I
(32%), C4H9CH=CHCl (5%) (cis/trans = 40:60), besides minor un-
known products (GC-MS data).
B. The reaction of bromine (160 mg, 1.00 mmol) and K[CF2=CFBF3]
(190 mg, 1.00 mmol) in CH2Cl2 suspension (1 mL) was performed at
≈20 °C for 24 h as above. The combined CH2Cl2 extracts contained
CF2Br–CFBr2 (0.08 mmol, 8%) and a trace of CF2Br–CFHBr (19F
NMR). Borate K[CF2Br–CFBrBF3] was isolated in 70% yield
(242 mg).
Reaction of [Bu4N][CF3CϵCBF3]: A solution of ICl (85 mg,
0.52 mmol) in CH2Cl2 (0.2 mL) was added dropwise to a solution of
[Bu4N][CF3CϵCBF3] (152 mg, 0.38 mmol) in CH2Cl2 (0.9 mL) at
≈20 °C over a period of 1 h. The 19F NMR spectrum showed the for-
mation of CF3CϵCI (0.34 mmol, 89%) (δ = –50.7 ppm) (proved by
the addition of the pure substance[42]) besides [Bu4N][BF4] {δ(F) =
1
C. K[CF2=CFBF3] (116 mg, 0.61 mmol) was suspended in CH2Cl2
(0.5 mL) in a quartz tube and bromine (99 mg, 0.61 mmol) was added.
The suspension was stirred at ≈20 °C for 9 h under irradiation with a
photo lamp (100 W). The mother liquor was separated. The solid part
was washed with CH2Cl2 (2ϫ2 mL). The combined extracts contained
CF2Br–CFBr2 (0.04 mmol, 7%) (19F NMR). The solid residue was
dried in vacuo and extracted with acetone. The extract was evaporated
to dryness yielding K[CF2Br–CFBrBF3] (135 mg, 0.39 mmol, 64%
yield).
–152 ppm [q, J(F, B) = 1 Hz]} (0.32 mmol, 84%).
Reaction of [Bu4N][C4H9BF3]: A solution of ICl (0.31 mmol) in
CH2Cl2 (1 mL) was added dropwise to a solution of [Bu4N][C4H9BF3]
(0.31 mmol) in CH2Cl2 (0.9 mL) at 20 °C. The color of ICl disap-
peared immediately after dropping. After the last drop a red-brownish
1
solution remained. The solution was stirred for 3 h at 20 °C. The H
and 19F NMR spectra showed the resonances of C4H9I (0.15 mmol,
48%), C4H10 (0.06 mmol, 19%), [Bu4N][BF4] {δ(F) = –152 ppm (s)}
(0.31 mmol, 100%) and a very broad resonance at δ = –132 ppm.
K[CF2Br–CFBrBF3]: 11B NMR (CH3CN): δ = 0.0 [dq 2J(B, F1) =
16, 1J(B, F) = 39 Hz]. 19F NMR (CH3CN): δ = –50.7 [qdd 4J(F2A
,
Reactions on the Surface of Potassium
Perfluoroalkenyltrifluoroborates with Chlorine in
Halocarbons
BF3) = 6, 3J(F2A, F1) = 18, 2J(F2A, F2B) = 167 Hz, 1F, F2A], –52.7
[qdd 4J(F2B, BF3) = 6, 3J(F2B,F1) = 21, 2J(F2B, F2A) = 167 Hz, 1F,
1
3
F2B], –138.5 (m, 1F, F1), –147.7 [q (1:1:1:1)dt, J(F, B) = 39, J(BF3,
Reaction of K[CF2=CFBF3]: Chlorine (4.5 mmol) was bubbled into a F1) = 6, 4J(BF3, F2) = 6 Hz, 3F, BF3] (conformer A, cf. reaction of
stirred suspension of K[CF2=CFBF3] (173 mg, 0.92 mmol) in CH2Cl2 [Bu4N][CF2=CFBF3] with Br2). NMR spectroscopic data in DMSO
Z. Anorg. Allg. Chem. 2012, 565–579
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
577

V. V. Bardin, N. Y. Adonin, H.-J. Frohn
are given in Table S2 (Supporting Information). Anal. for C2BBr2F6K amount of fluoroorganic compounds. The solid was washed with
ARTICLE
(347,73): calcd. C 6.91; Br 45.96; F 32.78%; found: C 6.8; Br 45.7;
F 33.0%.
CH2Cl2 (2 mL) and dried in vacuo to recover K[CF3CϵCBF3] (92 mg,
92%) (19F NMR).
CF2Br–CFBr2. 19F NMR (CH3CN): δ = –59.0 [d, 3J(F2, F1) = 17 Hz,
2F, F2], –70.4 [t, 3J(F1, F2) = 17 Hz, 1F, F1) {ref.[43] (in CF2Cl2)
(–36 °C): δ = –59.1 (2F F2), –68.9 (1F F1)}.
Reaction on the Surface of K[CF2=CFBF3] with Iodine
Chloride in Halocarbon
3
CF2Br–CFHBr: 19F NMR (CH2Cl2): δ = –59.6 [ddd, J(F2A, H1) =
A solution of ICl (1.13 mmol) in CH2Cl2 (5 mL) was added dropwise
to the stirred suspension of K[CF2=CFBF3] (174 mg, 0.92 mmol) in
CH2Cl2 (1 mL) at ≈20 °C. The suspension was stirred for 1.5 h and
centrifuged. The mother liquor was decanted. The dark violet solution
contained CF2=CFI (0.26 mmol, 31%) and unknown products (19F
NMR). The solid part was washed with CH2Cl2 (2ϫ2 mL), dried in
vacuo at ≈20 °C for 1 h and extracted with MeCN (2ϫ2 mL). The
solvent was removed under reduced pressure at 25 °C to give a yellow-
ish solid (122 mg). The 11B and 19F NMR spectra in CD3CN showed
the resonances of K[CF2=CFBF3] (0.07 mmol, 92% conversion),
K[CF2I–CFClBF3] (0.25 mmol, 29%) besides an admixture of pre-
sumably K[FC(O)–CFClBF3] (0.06 mmol, 7%) {signals at δ = 18.8
3, 3J(F2A, F1) = 24, 2J(F2A, F2B) = 172 Hz, 1F, F2A], –63.9 [ddd,
3J(F2B, H1) = 9, 3J(F2B, F1) = 21, 2J(F2B, F2A) = 172 Hz, 1F, F2B],
–149.4 [ddd, J(F1, H1) = 47, 3J(F1, F2A) = 24, J(F1, F2B) = 21 Hz,
2
3
1F, F2] {ref.[44] (in CCl3F): δ = –59.3 (1F, F2A), –63.8 (1F, F2B), –149.3
(1F, F1); J(F2A, H1) = 3.4, J(F2A, F1) = 24.0, J(F2A, F2B) = 172.5,
3
3
2
3J(F2B, H1) = 9.1, J(F2B, F1) = 20.6, J(F1, H1) = 47.0 Hz)}.
3
2
Attempted Reaction of K[trans-C4F9CF=CFBF3]: A. K[trans-
C4F9CF=CFBF3] (118 mg, 0.30 mmol) was suspended in a solution of
bromine (64 mg, 0.40 mmol) in CCl4 (1 mL) and stirred at 93–95 °C
(sealed tube) for 14 h. After cooling to 20 °C, the solid part was iso-
lated, washed with CH2Cl2 (4 mL), and dried in vacuo. The starting
material K[trans-C4F9CF=CFBF3] (113 mg, 96%) (19F NMR) was re-
covered.
4
3
[qd, J(F2, BF3) = 6, J(F2, F1) = 44 Hz, 1F, F2], –148.3 (m, 1F, F1),
4
3
–150.6 [ddq (1:1:1:1), J(BF3, F2) = 6, J(BF3, F1) = 10, 1J(F, B) =
38 Hz, 3F, BF3] (19F NMR) and at 0.8 [dq J(B, F1) = 15, J(B, F) =
2
1
39 Hz] (11B NMR)}.
B. K[trans-C4F9CF=CFBF3] (186 mg, 0.48 mmol) was suspended in a
solution of bromine (87 mg, 0.54 mmol) in CH2Cl2 (1.5 mL) and
stirred at ≈20 °C for 20 h. The solid part was separated, washed with
CH2Cl2 (2 mL), and dried in vacuo to give K[trans-C4F9CF=CFBF3]
(168 mg, 90%) (19F NMR).
2
K[CF2I–CFClBF3]: 11B NMR (CD3CN): δ = 0.6 [dq J(B, F1) = 15,
1J(B, F) = 38 Hz]. 19F NMR (CD3CN): δ = –54.2 [dd, J(F2A, F1) =
3
19, 2J(F2A, F2B) = 165 Hz, 1F, F2A], –57.4 [qdd 4J(F2B, BF3) = 7,
3J(F2B, F1) = 20, J(F2B, F2A) = 165 Hz, 1F, F2B], –147.0 (m, 1F, F1),
2
1
–147.4 [q (1:1:1:1), J(F, B) = 39 Hz, 3F, BF3].
Reaction of K[trans-C4H9CF=CFBF3]: A solution of bromine
(118 mg, 0.74 mmol) in CH2Cl2 (0.2 mL) was added dropwise to a
suspension of K[trans-C4H9CF=CFBF3] (98 mg, 0.43 mmol) in
CH2Cl2 (2 mL) at ≈20 °C within 5 min. The color of bromine disap-
peared within a few min. The suspension was stirred for 1 h, the
mother liquor was separated by centrifugation, washed with water and
dried with MgSO4. The 19F NMR spectrum showed the resonances of
C4H9CF=CFBr (cis/trans = 40:60) (0.03 mmol, 7%), C4H9CF=CFH
(cis/trans = 18:82) (0.07 mmol, 16%), C4H9CFBr–CFBr2 (0.20 mmol,
47%), and C4H9CFBr–CFHBr (0.07 mmol, 16%). The precipitate was
washed with CH2Cl2 and dried in vacuo. The acetone extract contained
only traces of fluoroorganics (19F NMR).
Reaction of trans-C4F9CF=CHF with Bromine
The heterogeneous mixture of trans-C4F9CF=CHF (1.0 g, 3.5 mmol)
and bromine (0.6 g, 3.6 mmol) was stirred in a quartz tube at 30 °C
under irradiation with
a super-high-pressure mercury lamp (λ
Ͼ365 nm, 240 W) (two lamps DRK 120) for 15 h. The bottom and
the upper phase contained cis-C4F9CF=CHF and C4F9CFBr–CHFBr.
The signals of trans-C4F9CF=CHF were not detected. After addition
of a new portion of bromine (0.6 g, 3.6 mmol) the irradiation was con-
tinued for 24 h. The reaction mixture was washed with aqueous
Na2S2O5, with water, and finally dried with MgSO4. The 19F NMR
spectrum showed the signals of C4F9CFBr–CHFBr and a trace of cis-
C4F9CF=CHF. Distillation gave pure C4F9CFBr–CHFBr (0.82 g,
0.85 mmol, 53%) (b. p. 135–138 °C).
Reaction of K[trans-C6H5CF=CFBF3]: A solution of bromine
(78 mg, 0.49 mmol) in CH2Cl2 (0.2 mL) was added dropwise to a sus-
pension of K[trans-C6H5CF=CFBF3] (71 mg, 0.28 mmol) in CH2Cl2
(2 mL) at ≈20 °C within 5 min. The suspension was stirred for 1 h, the
mother liquor was separated after centrifugation, washed with water
and dried with MgSO4. The 19F NMR spectrum showed the resonances
of trans-C6H5CF=CFBr (0.04 mmol, 14%) and C6H5CFBr–CFBr2
(0.21 mmol, 75%) besides minor amounts of unknown products. The
precipitate was washed with CH2Cl2 and dried in vacuo. The acetone
extract contained only traces of fluoroorganics (19F NMR).
C4F9CFBr–CHFBr: 1H NMR (CDCl3): δ = 6.80 [d, 2J(H1, F1) =
48 Hz, 1H, H1] (diastereomer A); 6.68 [dd, 3J(H1, F2) = 12, 2J(H1, F1)
= 48 Hz, 1H, H1] (diastereomer B) (A:B = 55:45). 19F NMR (CDCl3):
3
4
δ = –81.7 [tt, J(F6, F5) = 3, J(F6, F4) = 10 Hz, 3F, F6], –111.7 [md
2J(F3A, F3B) = 289 Hz, 1F, F3A], –114.0 [md 2J(F3B, F3A) = 289 Hz,
1F, F3B], –120.1 [md 2J(F4A, F4B) = 298 Hz, 1F, F4A], –121.0 [md
2J(F4B, F4A) = 298 Hz, 1F, F4B], –126.6 [md 2J(F5A, F5B) = 294 Hz,
1F, F5A], –127.2 [md 2J(F5B, F5A) = 294 Hz, 1F, F5B], –129.3 [md
Attempted Reaction of K[C4H9BF3]:
A solution of bromine
5
4
3J(F2, F1) = 41 Hz, 1F, F2], –146.0 [ttdd, J(F1, F4) = 3, J(F1, F3) =
(0.54 mmol) in CH2Cl2 (1.8 mL) was added to a suspension of
K[C4H9BF3] (78 mg, 0.47 mmol) in CH2Cl2 (1 mL) at ≈20 °C. The
red suspension was stirred for 6 h. The mother liquor contained only
traces of C4H9Br and C4H10 (1H NMR).
12, 3J(F1, F2) = 40, 1J(F1, H1) = 48 Hz, 1F, F1] (diastereomer A); –81.7
[tt, 3J(F6, F5) = 3, 4J(F6, F4) = 10 Hz, 3F, F6], –112.4 [md 2J(F3A, F3B
)
= 291 Hz, 1F, F3A], –112.9 [md 2J(F3B, F3A) = 291 Hz, 1F, F3B], –120.9
(m, 2F, F4), –126.9 (m, 2F, F5), –133.1 (m, 1F, F2), –143.9 [md J(F1,
2
Attempted Reaction of K[CF3CϵCBF3]: A suspension of salt
H1) = 48 Hz, 1F, F1] (diastereomer B) (A:B = 55:45). IR (neat): ν˜ =
K[CF3CϵCBF3] (100 mg, 0.50 mmol) and bromine (252 mg, 2991 (C-H), 1750, 1356, 1328, 1240, 1224, 1211, 1142, 1101, 1064,
1.57 mmol) was stirred in CH2Cl2 (1 mL) at ≈20 °C for 36 h. The 19F
NMR spectrum of the decanted mother liquor showed a negligible
1033, 911, 812, 778, 743, 712, 700, 662, 629, 595, 577, 531 cm–1. MS
(EI) calcd. for C6HBr2F11 439.82703 (79Br), found 439.82704 (79Br).
578
www.zaac.wiley-vch.de
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2012, 565–579

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Supporting Information (see footnote on the first page of this article):
Solubilities of selected organylfluoroborate salts in different solvents.
NMR spectroscopic data of K[C4H9CϵCBF3] in [D6]acetone.
Acknowledgement
We gratefully acknowledge financial support by the Deutsche For-
schungsgemeinschaft, the Russian Foundation for Basic Research, the
Fonds der Chemischen Industrie, and Solvay Fluor und Derivate
GmbH for donation of PFB.
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Received: June 21, 2011
Published Online: September 29, 2011
Z. Anorg. Allg. Chem. 2012, 565–579
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
579