On the chemistry of fluoroorgano derivatives of group 13 elements. 1 The reactions of perfluoroiodoalkanes and pentafluoroiodobenzene with triethylindium - Synthesis and characterization of In(C2H5)2(C6F5) · N(C2H5)3 and In(C2H5)2(i-C3F7

Article abstract of DOI:10.1002/(SICI)1521-3749(1998120)624:12<2015::AID-ZAAC2015>3.0.CO;2-F

R_fI (R_f = C₂F₅, n-C₃F₇, n-C₄F₉, n-C₆F₁₃, i-C₃F₇, C₆F₅) and In(C₂H₅)₃ react in a variety of solvents with formation of the derivatives In(C₂H₅)₂R_f as the major products. However, strong bases like N(C₂H₅)₃ are required to stabilize the compounds. In(C₂H₅)₂(C₆F₅) · N(C₂H₅)₃ and In(C₂H₅)₂(i-C₃F₇) · N(C₂H₅)₃ were isolated from the reactions in the presence of N(C₂H₅)₃ as NMR spectroscopically pure oily liquids in moderate yields (64% and 40%). With exception of C₂F₅I all perfluoroiodo-n-alkanes reacted with In(C₂H₅)₃ to give the corresponding products, which contained impurities up to 25% that could not be separated by common methods. In the presence of N(C₂H₅)₃, C₂F₅I reacted with In(C₂H₅)₃ with formation of In(C₂H₅)(C₂F₅)I · N(C₂H₅)₃ as the major product, in the absence of N(C₂H₅)₃ mainly In(CH₂CH₂CF₂CF₃)₂I was formed. All reactions described have in common that In(C₂H₅)₂F precipitated from the reaction mixtures irrespective of the iodo component. All derivatives can be stored for several months at temperatures below -25°C, at ambient temperature they decompose within a few days giving R_fH as the only fluorine containing compound.

Full text of DOI:10.1002/(SICI)1521-3749(1998120)624:12<2015::AID-ZAAC2015>3.0.CO;2-F

Z. anorg. allg. Chem. 624 (1998) 2015±2020
Zeitschrift fuÈr anorganische
und allgemeine Chemie
WILEY-VCH Verlag GmbH 1998
On the Chemistry of Fluoroorgano Derivatives of Group 13 Elements. 1
The Reactions of Perfluoroiodoalkanes and Pentafluoroiodobenzene
with Triethylindium ± Synthesis and Characterization
of In(C2H5)2(C6F5) ´ N(C2H5)3 and In(C2H5)2(i-C3F7) ´ N(C2H5)3
and Spectroscopic Evidence for Bis(3,3,4,4,4-pentafluorobutyl)indium Iodide
Zel-Ho Choi and Wieland Tyrra*
KoÈln, Institut fuÈr Anorganische Chemie der UniversitaÈt
Received June 11th, 1998.
Abstract. RfI (Rf = C2F5, n-C3F7, n-C4F9, n-C6F13, i-C3F7,
C6F5) and In(C2H5)3 react in a variety of solvents with for-
mation of the derivatives In(C2H5)2Rf as the major products.
However, strong bases like N(C2H5)3 are required to sta-
bilize the compounds. In(C2H5)2(C6F5) ´ N(C2H5)3 and
In(C2H5)2(i-C3F7) ´ N(C2H5)3 were isolated from the reac-
tions in the presence of N(C2H5)3 as NMR spectroscopically
pure oily liquids in moderate yields (64% and 40%). With
exception of C2F5I all perfluoroiodo-n-alkanes reacted with
In(C2H5)3 to give the corresponding products, which con-
tained impurities up to 25% that could not be separated by
common methods. In the presence of N(C2H5)3, C2F5I re-
acted with In(C2H5)3 with formation of In(C2H5)(C2F5)I ´
N(C2H5)3 as the major product, in the absence of N(C2H5)3
mainly In(CH2CH2CF2CF3)2I was formed. All reactions de-
scribed have in common that In(C2H5)2F precipitated from
the reaction mixtures irrespective of the iodo component.
All derivatives can be stored for several months at tempera-
tures below ±25 °C; at ambient temperature they decompose
within a few days giving RfH as the only fluorine containing
compound.
Keywords: Diethyl(perfluoroorgano)indium compounds; nmr
spectra
Zur Chemie von Fluororganoderivaten der Elemente der Gruppe 13. 1.
Die Reaktionen von Perfluoriodalkanen und Pentafluoriodbenzol mit
Triethylindium ± Synthese und Charakterisierung von In(C2H5)2(C6F5) ´ N(C2H5)3
und In(C2H5)2(i-C3F7) ´ N(C2H5)3 und der spektroskopische Nachweis
von Bis(3,3,4,4,4-pentafluorbutyl)indiumiodid
InhaltsuÈbersicht. RfI (Rf = C2F5, n-C3F7, n-C4F9, n-C6F13, i-
C3F7, C6F5) und In(C2H5)3 reagieren in vielen LoÈsungsmit-
teln unter Bildung der Verbindungen In(C2H5)2Rf als
Hauptprodukte. Starke Basen wie N(C2H5)3 werden jedoch
benoÈtigt, um die Produkte zu stabilisieren. In(C2H5)2(C6F5) ´
N(C2H5)3 und In(C2H5)2(i-C3F7) ´ N(C2H5)3 wurden aus Re-
aktionsansaÈtzen in Gegenwart von N(C2H5)3 als NMR-spek-
troskopisch reine, oÈlige FluÈssigkeiten in maÈûigen Ausbeuten
(64% bzw. 40%) isoliert. Mit Ausnahme von C2F5I reagieren
alle Perfluoriod-n-alkane mit In(C2H5)3 zu den entsprechen-
den Verbindungen, jedoch waren diese mit bis zu 25% durch
auf einfachem Wege nicht abtrennbare Substanzen ver-
unreinigt. In Gegenwart von N(C2H5)3 wird bei der Um-
setzung von C2F5I mit In(C2H5)3 als Hauptprodukt
In(C2H5)(C2F5)I ´ N(C2H5)3 gebildet; in Abwesenheit von
N(C2H5)3 hauptsaÈchlich In(CH2CH2CF2CF3)2I. UnabhaÈngig
vom eingesetzten Iodderivat wird bei allen Umsetzungen
In(C2H5)2F als Beiprodukt gebildet, das aus den Reaktions-
mischungen ausfaÈllt. Alle Verbindungen koÈnnen mehrere
Monate bei Temperauren unterhalb von ±25 °C gelagert wer-
den; bei Raumtemperatur wird eine Zersetzung innerhalb
weniger Tage beobachtet. RfH kann als einziges fluorhalti-
ges Produkt identifiziert werden.
* Correspondence Address:
Dr. W. Tyrra
Institut fuÈr Anorganische Chemie
UniversitaÈt zu KoÈln
Greinstr. 6
D-50939 KoÈln
Fax: 02 21 / 4 70-51 96
e-mail: tyrra@uni-koeln.de

2016
Z. anorg. allg. Chem. 624 (1998)
Introduction
The precipitate primarily formed in all reactions
was identified as In(C2H5)2F although the resulting
elimination products, neither fluoroolefins nor arenes
or their oligomers, respectively, were not found except
for hexafluoropropene in reactions with i-C3F7I.
In(C2H5)2F was identified by its NMR-spectra (cp. [9,
10]), elemental analysis and mass spectrum.
The mass spectrometric decay is comparable with
that reported for In(CH(CH3)2)2F [10]. The mass
spectrum (EI, 20 eV) showed the peak [In3(C2H5)5F3]+
as the fragment of highest mass (m/e = 547) in intensi-
ties varying between 8.5% and 18.9%. The peaks of
highest intensity were in all spectra those of
[In2(C2H5)3F2]+ (m/e = 355; intensities 60.9% to
99.3%) and [In(C2H5)2]+ (m/e = 173) being the basis
peak in all spectra. The ions detected reveal that
In(C2H5)2F appears to be trimeric in the gas-phase
and probably as a solid.
Alkyl-perfluoroorgano group exchange reactions are
successfully used in the synthesis of perfluoralkyl zinc
[1] and cadmium reagents [2±4]. The reactions of the
higher perfluoroiodoalkanes with Cd(CH3)2 proceed
selectively and quantitatively without any base pre-
sent [3], whereas reactions with CF3I [4] and C2F5I [5]
gave an incomplete exchange or yielded a great num-
ber of by-products. However, use of Cd(C2H5) as a
starting material allowed the synthesis of donor-free
Cd(CF3)2 [4].
Examples for successful alkyl-perfluoroalkyl group
exchange reactions in main group chemistry are e. g.
those of Te(CH3)2 and RfI to yield Te(CH3)Rf [6]
and of Bi(CH3)3 and CF3I giving mixtures of
Bi(CH3)2(CF3) and Bi(CH3)(CF3)2 [7].
Results and Discussion
The total absence of hints for [N(C2H5)4]I cannot be
explained. However, it must be suggested that
In(C2H5)2Rf derivatives and In(C2H5)3 are strong Le-
wis-acids that completely bond the stoichiometric
amounts of N(C2H5)3. It remains unintelligible that
even in the presence of a twofold or threefold excess of
N(C2H5)3 no spectroscopic evidence for the quarter-
nary ammonium salt was found. Therefore it might be
suggested that this system efforts a higher temperature
than room temperature for ammonium salt formation.
Comparative investigation by our group [11] and lit-
erature data [12±14] proof strong interactions of RfI
and N(C2H5)3 although no evidence for the formation
of salts with the discrete cation [N(C2H5)3Rf]+ had
been found.
The reactions of triethylindium and
perfluoroiodoorganics in the presence of triethylamine
Alkyl-perfluoroalkyl indium derivatives are unknown
so far with one exception. Schumann et al. [8]
described the synthesis of bis[(3-dimethylamino)-
propyl](heptafluoroisopropyl)indium starting with
In(i-C3F7)Br2 and Cd(CH2CH2CH2N(CH3)2)2.
The reactions of RfI with In(C2H5)3 with the excep-
tion of those of C2F5I had in common, that one ethyl
group was exchanged for one perfluoroorgano group,
even if a large excess of the perfluoroiodoalkane was
used.
The formation of the detected products indicates re-
actions via SET-processes [15, 16].
In(C2H5)3 + RfI → In(C2H5)2Rf + C2H5I
(Donor molecules were omitted for clarity.)
SET
R3In + RfI
RfI± ´
!
!
R3In+ ´ + RfI± ´
Rf´ + I±
After testing several complexing ligands (ethers, poly-
ethers, DMF, CH3CN, pyridine), N(C2H5)3 turned out
to be the most suitable base in these reactions.
In all reactions, mainly performed in n-hexane solu-
tion, two layers (except for i-C3F7I) were separated
on stirring, covering a white precipitate. The two
layers were roughly analyzed in advance by their 19F-
NMR-spectra.
dissociation
dissociation
R3In+ ´
!
!
!
!
!
!
R2In+ + R´
Rf± + R3In+ ´
R2InRf
SET
addition
SET
Rf´ + R3In
Rf± + R2In+
R´ + RfI
R+ + I±
R+ + RfI± ´
In the case of C6F5I in the upper layer N(C2H5)3,
In(C2H5)2I, traces of In(C2H5)2(C6F5) ´ N(C2H5)3 and
C6F5H were detected, the bottom layer gave exclu-
sively evidence for In(C2H5)2(C6F5) ´ N(C2H5)3 as the
only fluorine containing compound.
In reactions with i-C3F7I separation of two layers
was not observed. In(C2H5)2(i-C3F7) ´ N(C2H5)3,
i-C3F7H, In(C2H5)2I and hexafluoropropene were de-
tected.
In reactions with perfluoroiodo-n-alkanes two
layers were formed. The upper layer consisted mainly
of n-hexane, RfH and RfI, the bottom layer of
In(C2H5)Rf derivatives and In(C2H5)2I.
addition
addition
RI
R2In+ + I±
R2InI
It cannot be excluded that the formation of
In(C2H5)2I might result from
In(C2H5)3 + C2H5I → In(C2H5)2I + n-C4H10
probably also under SET-conditions, because the reac-
tion of In(C2H5)3 and CHnCl4±n (n = 0, 1, 2) is a con-
venient route for the synthesis of In(C2H5)2Cl [17].
However, n-C4H10 had never been detected in 1H-
NMR spectra recorded at room temperature.

Zel-Ho Choi, W. Tyrra, On the Chemistry of Fluoroorgano Derivatives of Group 13 Elements
2017
From the reaction mixtures In(C2H5)2(C6F5) ´
N(C2H5)3 and In(C2H5)2(i-C3F7) ´ N(C2H5)3 were iso-
lated and characterized by their NMR and mass spec-
tra.
In(C2H5)2F. However, the isolation of the pentafluoro-
phenylindium derivative failed.
Reactions with perfluoroiodoalkanes gave spectro-
scopic evidence for several In(C2H5)Rf compounds,
but all attempts to isolate any of the indium com-
pounds failed.
The NMR spectra showed that the products, highly
viscous liquids, were sufficiently pure substances.
Attempts to determine the fluorine content failed
because the derivatives rapidly destroyed the gelatine
capsule required for the decomposition processes.
The mass spectrum (EI, 20 eV, 150 °C) of
In(C2H5)2(C6F5) ´ N(C2H5)3 exhibited [In(C2H5) ´
(C6F5)]+ (m/e = 311, intensity 61.4%) as the fragment
of highest mass. The mass spectrometric decay of
In(C2H5)2(i-C3F7) ´ N(C2H5)3 indicated the primary
loss of N(C2H5)3 because spectra recorded at 20 eV, at
temperatures up to 150 °C only showed the ion
[N(C2H5)3]+ and fragments of triethylamine.
Rising temperature to 190 °C gave evidence for
indium containing ions. As ions of highest masses
[In3(C2H5)3(C3F7)2F]+ (m/e = 789, intensity 60.0%)
and [In3(C2H5)3(C3F7)]+ (m/e = 601, intensity 14.7%)
were detected indicating the formation of
[In(C2H5)2(C3F7)]3 after loss of N(C2H5)3.
The highly viscous liquids obtained from reactions
of In(C2H5)3 and n-C3F7I, n-C4F9I and n-C6F13I were
only analyzed by 19F-NMR-spectroscopy showing that
the acquired products had been formed but were im-
pured with up to 20% of unidentified indium contain-
ing derivatives and n-C6F13H in reactions with n-
C6F13I.
However, the different reaction behaviour of C2F5I
cannot be explained. In(C2H5)(C2F5)I ´ N(C2H5)3 was
formed as the major product; elemental analysis as
well as 13C- and 1H-NMR spectra exhibited that
In(C2H5)2I had also been formed. The upper layer
showed spectroscopic evidence for C2F5I, C2F5H and
probably CF3CF2CH2CH3 as the only fluorine con-
taining compounds.
In reactions of In(C2H5)3 with C2F5I and i-C3F7I
spectroscopic evidence for Wurtz-type couplings
was found. For instance, the mass spectrum (EI,
20 eV, 30 °C) of the condensate of the reaction with
i-C3F7I showed as the peak of highest mass m/e =
324 (intensity 16.2%) which was assigned to
[(CF3)2CFCH2CH2I]+; characteristic fragments were
found at m/e = 197 (3.5%) [(CF3)2CFCH2CH2]+,
m/e = 177 (9.8%) [(CF3)2C=CHCH2]+, m/e = 88
(13.3%) [CF4]+ and m/e = 69 (18.9%) [CF3]+. The
basis peak was detected at m/e = 28, [C2H4]+ or [N2]+.
The reaction of In(C2H5)3 and C2F5I in n-hexane or
without any solvent also led to an unexpected result.
The NMR-spectroscopic investigations as well as the
mass spectra exhibited that compounds with
CF3CF2CH2CH2In-units have been formed.
In(C2H5)3 + C2F5I → In(CH2CH2CF2CF3)3±xIx + . . .
(x = 0, 1, 2)
NMR spectroscopic and mass spectrometric evidence
was also found for di- or trimeric In(C2H5)(C2F5)-de-
rivatives that precipitated as white solids from the
reaction mixtures. Similar results were obtained work-
ing up the reaction mixture of In(C2H5)2Cl and
Cd(C2F5)2 ´ D in various solvents [18]. However, aque-
ous working up to obtain the In(CH2CH2CF2CF3)-
compounds might have destroyed some of the prima-
rily formed derivatives.
The evidence for an indium derivative containing
the CF3CF2CH2CH2-ligand was supported by the
NMR spectra which matched well with expectations.
In the 19F-NMR spectrum the CF3-group was de-
tected at ±85.4 ppm, m, the CF2-group at ±121.0 ppm,
NꢀC2H5†
3
In(C2H5)3 + C2F5I
! In(C2H5)(C2F5)I ´ N(C2H5)3;
3
t, J(19F±1H) = 18 Hz. The multiplicity of both signals
In(C2H5)2I; C2F5H; CF3CF2CH2CH3; . . .
was reduced to singlets in proton decoupling experi-
3
ments. The absolute value of the J(19F±1H)-coupling
Replacement of N(C2H5)3 in In(C2H5)2(C6F5) ´
N(C2H5)3 by As(C2H5)3 quantitatively yielded the 1 : 1
± adduct with the arsane, which was characterized by
its NMR spectra.
is in excellent agreement with values of 18 Hz re-
ported for [I(C6H5)CH2CF2CF3]OSO2CF3 [19] and
CH3C6H4CH2CF2CF3 [20].
The 13C{1H}-NMR spectrum displays the typical
splitting of a CF3CF2CH2CH2-ligand. The resonance
of the CF3-group is centred at 119.7 ppm and charac-
teristically split into a quartet of triplets. The charac-
teristic splitting into a triplet of quartets is also ob-
served for the CF2-group, which, however is detected
approximately 10 ppm downfield from that of a CF2-
group directly bonded to indium (s. experimental
part) but in the region of 13C-NMR chemical shifts of
CF3CF2-groups bond to sp3-hybridized carbon atoms
The reactions of triethylindium
and perfluoroiodoalkanes in the absence of a base
All reactions in absence of a base proceeded less se-
lectively than in the presence of N(C2H5)3. Dilution
with n-hexane required long reaction times (in some
cases 7 days) for a complete consumption of RfI.
In(C2H5)2F was formed in each reaction.
The reaction with C6F5I in n-hexane gave evidence
for the formation of In(C2H5)2(C6F5), C6F5H and
(2'-pentafluoroethyl-1',2'-[dihydropyridine]-4-nitrobenz
-
amide, d(CF2) 114.2 ppm, 2J(19F±13C) = 36 Hz) [21].

2018
Z. anorg. allg. Chem. 624 (1998)
the reaction mixture was slowly warmed to ambient tem-
perature overnight. Two organic layers were formed and
additionally a white solid had precipitated in reactions with
perfluoroiodoalkanes which was identified as trimeric,
[In(C2H5)2F]3. The upper phase consisted of n-hexane, RfH,
some RfI and in the case of i-C3F7I of perfluoropropene.
The bottom layer mainly consisted of In(C2H5)2(Rf) ´
N(C2H5)3, some In(CH2CH3)2I and RfH. In all cases the
bottom layer was worked up.
The triplet-splitting
of the b-CH2-resonance
(2J(19F±13C) = 22 Hz) centred at 26.7 ppm also sup-
ports this suggestion. The assignment of the α-CH2-re-
sonance (d 3.1 ppm) to a CH2-group directly bonded
to indium is based on the broadening of the signal due
to the influence of the quadrupole moments of both
indium isotopes [22] as well as the chemical shift,
which is characteristic for α-CH2-groups directly
bonded to metal centres.
Best results were achieved using n-hexane as the solvent
(see Table 1).
1
The H-NMR spectrum is dominated by a triplet of
triplets centred at 1.9 ppm (3J(19F±1H) = 18 Hz,
3J(1H±1H) = 8 Hz) and
a
triplet at 0.4 ppm
(3J(1H±1H) = 8 Hz). Both, chemical shifts and split-
tings indicate 3,3,4,4,4-pentafluorobutyl group
bonded to indium.
Isolation and characterization of [In(C2H5)2F]3. Diethylin-
dium fluoride precipitated from all mixtures of In(C2H5)3
and perfluoroiodo alkanes. It was separated by filtration and
a
1
analyzed by 19F-, H- and 13C-NMR spectroscopy, as well as
mass spectrometry and elemental analyses. In some cases
small amounts of In(C2H5)2I were detected in the mass spec-
tra and by elemental analysis (iodine content < 5%).
Additionally, on the basis of the peaks of highest
mass (MS, 20 eV, 60 °C) i. e. 409 (28.0%,
[In(C2H4C2F5)2]+) and 389 (18.9%; [In(C2H4C2F5)I]+)
it must be suggested that In(CH2CH2CF2CF3)2I had
been formed as the major product. However, a me-
chanistic explanation for the derivatives formed in re-
actions of In(C2H5)3 and C2F5I cannot be given.
Analytical data of [In(C2H5)2F]3 (product of the reaction of
In(C2H5)3 and i-C3F7I in the absence of N(C2H5)3). Elemen-
tal analysis for C12H15In3F3: found (calculated) In: 56.8%
(59.8%), F: 10.2% (9,9%).
NMR-data of [In(C2H5)2F]3 in (CD3)2SO: 19F: d(F) ±167.4 ppm. 1H:
d(CH3) 1.1 ppm, t, d(CH2) 0.4 ppm, q, 3J(1H±1H) = 8.0 Hz. 13C{1H}:
d(CH3) 11.2 ppm, d(CH2) 9.9 ppm. MS (20 eV, 120 °C): 547 (18.9%,
[In3(C2H5)5F3]+), 463 (42.4%, ?); 371 (11.9%, ?), 365 (7.0%,
Conclusion
[In2(C2H5)4F]+),
355
(60.9%,
[In2(C2H5)3F2]+);
297
(21.0%,
The reactions of In(C2H5)3 and perfluoroiodo organ-
ics are the first examples of a successful ethyl-per-
fluoroorgano group exchange in indium chemistry.
However, the scope is limited and cannot be regarded
as a general method for the selective synthesis of dial-
kyl(perfluoroorgano)indium derivatives on a prepara-
tive scale. The reactions with C2F5I gave unexpected
results that cannot be explained at present time.
[In2(C2H5)2F2]+), 249 (9.1%, [In2F]+?), 209 (18.2%, ?), 203 (35.7%,
[In(C2H5)3 + H]+?), 179 (7.7%, ?), 173 (100%, [In(C2H5)2]+), 144 (7.7%,
[In (C2H5)]+), 115 (59.5%, [In]+).
Fragments with masses less than 40 m/e and intensities less
than 5% were omitted. Missing assignments indicated by
question marks might be referred to iodine containing frag-
ments. See above.
Entries 1 and 2: The bottom layer was distilled in vacuo (ca.
1 ´ 10±2 Torr) at 90 °C (oil bath: 140 °C). An oily liquid was
obtained (1.4 g, 63.5%, entry 1).
Experimental
Elemental analysis for C16H25F5InN: [found (calculated)]:
In 21.92% (26.03%).
Gelatine capsules that are necessary for the combustion
to determine the fluorine and nitrogen content were affected
by the compound disintegrating the material. Therefore,
only the indium content could be determined.
All reactions were carried out in a dry nitrogen atmosphere
using Schlenk-techniques. Solvents were carefully dried and
purified according to literature procedures [23]. In(C2H5)3
and As(C2H5)3 were prepared by literature methods [24, 25].
Perfluoroiodo organics were purchased from ABCR (C2F5I,
n-C3F7I, C6F5I), Merck-Schuchardt (n-C4F9I, n-C6F13I) or
Fluka (i-C3F7I) and used after distillation in vacuo at room
temperature.
Table 1 Conditions for the reactions
The NMR spectra were recorded on the Bruker spectro-
meters AC 200 and AMX 300 operating at 200.1 MHz, and
300.1 MHz, respectively. CCl3F was used as an external stan-
dard in the 19F-NMR spectra. The signals of the deuterated
Entry
RfI
RfI
ml (mmol)
In(C2H5)3
ml (mmol)
N(C2H5)3
ml (mmol)
n-hexane
ml
1
2
C6F5I
C6F5I
i-C3F7I
i-C3F7I
i-C3F7I
C2F5I
0.67 (5.0)
0.40 (3.0)
0.71 (5.0)
0.71 (5.0)
1.07 (7.5)
1.23 g (5.0) 0.80 (5.0)
1.48 g (6.0) 0.80 (5.0)
1.44 (10.0)
1.72 (10.0)
2.16 (10.0)
0.80 (5.0)
0.40 (1.5)
0.80 (5.0)
0.40 (1.5)
0.40 (1.5)
0.70 (5.0)
0.40 (2.9)
0.70 (5.0)
0.70 (5.0)
1.04 (7.5)
0.70 (5.0)
1.40 (10.0)
1.40 (10.0)
1.40 (10.0)
1.40 (10.0)
10
10
10
10
10
10
20
10
10
10
1
solvents were used as internal standards in the H- and 13C-
3a)
4
NMR spectra and referenced to Si(CH3)4. Mass spectra
were recorded on a modified Varian MAT CH5 spectro-
meter. All assignments are based on the following isotopes:
1H, 12C, 14N, 19F, 115In, 127I.
5b)
6
7
8
9
C2F5I
n-C3F7I
n-C4F9I
n-C6F13
1.60 (10.0)
1.60 (10.0)
1.60 (10.0)
The reactions of In(C2H5)3 and RfI in the presence
of N(C2H5)3
10
I
a)
The reactions were also performed in glyme, tetraglyme, diethylether
and dichloromethane.
General procedure. N(C2H5)3 and RfI were dropped to a
solution of In(C2H5)3 in n-hexane at ±78 °C. While stirring,
b)
The reactions were also performed in tetraglyme and dichloromethane.

Zel-Ho Choi, W. Tyrra, On the Chemistry of Fluoroorgano Derivatives of Group 13 Elements
2019
MS (20 eV, 55 °C): 491 (6.7%, [In(C2H5)(C2F5)I ´ N(C2H5)3]+), 393 (3.2%,
[In(C2H5)2(C2F5) ´ N(C2H5)3]+), 390 (2.8%, [In(C2H5)(C2F5)I]+), 300
(3.5%, [In(C2H5)2I]+), 271 (17.1%, [In(C2H5)I]+), 242 (4.6%, [InI]+), 179
(100%, [InC2H2F2]+), 173 (29.2%, [In(C2H5)2]+), 144 (13.1%,
[In(C2H5)]+), 130 (19.2%, [InCH3]+), 115 (100%, [In]+), 100 (11.5%,
[C2F4]+ or [N(C2H5)2(C2H4)]+), 86 (8.5%, [N(C2H5)2CH2]+), 69 (13.8%,
[CF3]+), 58 (3.1%, [C3H8N]+ or [C4H10]+).
Table 2 19F-NMR-data of In(C2H5)2(C6F5) ´ N(C2H5)3 in
different solvents
Solvent
d(F-2,6)
d(F-4)
d(F-3,5)
n-hexane
C6D6
CDCl3
±114.7
±115.5
±116.0
±116.3
±154.9
±156.1
±156.7
±157.2
±160.0
±161.2
±161.7
±161.9
As(C2H5)3
While stirring the product mixture at room temperature, the
liquid became pale brown and a white solid precipitated,
which was identified as a mixture of In(C2H5)2F and
In(C2H5)2I.
NMR data of In(C2H5)2(C6F5) ´ N(C2H5)3 in C6D6. 19F: see
Table 1.
Entries 8±10: In(C2H5)3, N(C2H5)3, RfI and n-hexane were
combined at ±78 °C. The mixture was slowly warmed to
room temperature. Small amounts of In(C2H5)2F precipi-
tated. During stirring the mixture for 7 days at ambient tem-
perature, two layers formed. The upper layer contained only
traces of fluorinated products. The bottom layer was worked
up. After filtration of In(C2H5)2F all volatile compounds
mainly n-hexane, RfI and RfH were distilled off. The remain-
ing brown oils were analyzed by their 19F-NMR spectra
(CH2Cl2).
1H: d 2.72 ppm, q, N(CH2CH3), 3J(1H±1H) = 7.2 Hz, 6 H; d 1,25 ppm, t,
In(CH2CH3), 3J(1H±1H) = 7.9 Hz, 6 H; d 1.09 ppm, t, N(CH2CH3),
3J(1H±1H) = 7.2 Hz, 9 H; d 0.60 ppm, q, In(CH2CH3), 3J(1H±1H) = 7.9 Hz,
4 H.
13C{19F}: d(C-2,6) 148.8 ppm, d(C-4) 140.4 ppm, d(C-3,5) 136.8 ppm,
d(C-1) 123.0 ppm, d(NCH2CH3) 47.5 ppm, d(InCH2CH3) 12.5 ppm,
d(NCH2CH3) 10.4 ppm, d(InCH2CH3) 7.9 ppm.
MS (20 eV, 150 °C); 311 (61.4%, [In(C2H5)(C6F5)]+, 173 (54.3%,
[In(C2H5)2]+), 168 (17.9%, [C6F5H]+), 144 (12.9%, [In(C2H5)]+), 115
(80.7%, [In]+), 101 (20.0%, [N(C2H5)3]+), 86 (100%, [C5H12N]+), 58
(30.7%, [C3H8N]+ or [C4H10]+).
Entries 3±5: The bottom layer was separated. The oily
product isolated after distillation was identified as
In(C2H5)2(i-C3F7) ´ N(C2H5)3 on the basis of NMR spectro-
scopic investigations. The yields were ca. 50% in any case.
19F-NMR data of In(C2H5)2(n-C3F7) ´ N(C2H5)3: d(CF3) ±79.2 ppm,
d(α-CF2) ±119.8 ppm, d(b-CF2) ±123.1 ppm. The further signals at ±79.0,
±116.4, ±118.5, ±121.6, ±122.6 ppm (integrative ratio In(C2H5)2(n-C3F7) ´
N(C2H5)3 : other products = 5 : 1) might be assigned to In(C2H5)(n-C3F7) ´
N(C2H5)3 and In(n-C3F7)I2 ´ N(C2H5)3 [26].
In(C2H5)2(n-C4F9) ´ N(C2H5)3: d(CF3) ±81.0 ppm, d(α-CF2) ±119.3 ppm,
d(b-CF2) ±125.6 ppm, d(c-CF2) ±119.6 ppm. Further signals occurred around
±118 ppm (integrative ratio α-CF2 : other products = 4 : 1).
In(C2H5)2(n-C6F13) ´ N(C2H5)3: d(CF3) ±81.2 ppm, d(α-CF2) ±118.5 ppm,
d(further CF2-groups) ±119.1, ±121.7, ±122.7, ±126.2 ppm. Further low inten-
sity resonance are located around ±117 ppm (integrative ratio α-CF2 : other
products = 20 : 1).
NMR data of In(C2H5)2(i-C3F7) ´ N(C2H5)3 in CH2Cl2 (ex-
ternal lock: (CD3)2CO)
19F: d ±70.2 ppm, d, 3J(19F±19F) = 13.0 Hz, In(C2H5)2 ´ (CF(CF3)2) ´
N(CH2CH3)3, 6 F, d ±215.8 ppm, broad, In(C2H5)2(CF ´ (CF3)2) ´
N(C2H5)3, 1 F.
1H: d 2.3 ppm, q, N(CH2CH3)3, 6 H, d 1.3, t, In(CH2CH3)2, 6 H; d 0.8,
q, N(CH2CH3), 9 H; d 0.4, q, In(CH2CH3)2, 4 H. The absolute values of
the 3J(1H±1H) couplings were 8.0 Hz (In) and 7.2 Hz (N), respectively.
13C: 125.8 ppm, qm, 1J(19F±13C) = 257 Hz, 2J(19F±13C) = 23 Hz,
In(CH2CH3)2(CF(CF3)2) ´ N(CH2CH3)3, d 101.8 ppm, dm, 1J(19F±13C) =
210 Hz, 2J(19F±13C) = 42 Hz, In(CH2CH3)2(CF(CF3)2) ´ N(CH2CH3)3,
d 47.2 ppm, t, 1J(13C±1H) = 132 Hz, In(CH2CH3)2(CF(CF3)2) ´ N(CH2CH3)3,
The synthesis of In(C2H5)2(C6F5) ´ As(C2H5)3
d 12.3 ppm,
qt,
1J(13C±1H) = 123 Hz,
In(CH2CH3)2(CF(CF3)2) ´
N(CH2CH3)3, d 9.6 ppm, q (broad), 1J(13C±1H) = 127 Hz, In(CH2CH3)2 ´
In(C2H5)2(C6F5) ´ N(C2H5)3 was dissolved in As(C2H5)3 at
room temperature. The mixture was stirred overnight. All
volatile components were distilled off in vacuo at ambient
temperature during 48 hours. The condensate contained
traces of C6F5H as the only fluorine containing component.
The remaining colourless oil was investigated by NMR spec-
troscopy.
(CF(CF3)2) ´ N(CH2CH3)3, d 5.2 ppm,
In(CH2CH3)2(CF(CF3)2) ´ N(CH2CH3)3.
t
(broad), 1J(13C±1H) = 125 Hz,
The mass spectrum (20 eV, 190 °C) gave evidence for poly-
mers as it is known for mixed alkyl(perfluoroalkyl)gallium
derivatives [26].
Entries 6 and 7: The bottom layer was analyzed after distil-
ling all volatile components (n-hexane, C2F5H, excess C2F5I)
in vacuo.
NMR data of In(C2H5)2(C6F5) ´ As(C2H5)3 in CH2Cl2 (ex-
ternal lock (CD3)2CO)
The NMR-spectra suggested that at least three In(C2F5)-
derivatives were formed. On the basis of the elemental ana-
lysis as well as the mass spectra the main product had to be
proposed to be In(C2H5)(C2F5)I ´ N(C2H5)3 impured by
In(C2H5)2I.
19F: d(F±2,6) ±116.0 ppm, d(F-4) ±157.1 ppm, d(F±3,5) ±161.9 ppm.
1H: d(AsCH2CH3) 1.63 ppm, d(InCH2CH3) 1.29 ppm, d(AsCH2CH3)
1.18 ppm, d(InCH2CH3) 0.49 ppm.
Elemental analysis for the product obtained (viscous liq-
uid).
The reactions of In(C2H5)3 and RfI in the absence of a base
The general procedure corresponded with that described for
reactions in the presence of N(C2H5)3.
In
F
N
I
All reactions (Entries 1±6, 8±10) were carried out in 10 ml
n-hexane or without solvent. In entry 7 15 ml of a 10/1 n-
hexane/(C2H5)2O mixture were used. The results obtained
did not differ from the others.
found
calculated for
26.7%
14.9%
3.6%
28.1%
C
C
10H20F5IInN
10H25IInN
23.4%
28.7%
19.3%
±
2.9%
3.5%
25.9%
31.7%

2020
Z. anorg. allg. Chem. 624 (1998)
13C{1H}: d 119.7 ppm, qt, 1J(19F±13C) = 285 Hz, 2J(19F±13C) = 37 Hz,
Table 3 Conditions for the reactions
In(CH2CH2CF2CF3)2I;
d 116.7 ppm,
tq,
1J(19F±13C) = 250 Hz,
2J(19F±13C) = 37 Hz, In(CH2CH2CF2CF3)2I; d 26.7 ppm, t, 2J(19F±13C) =
Entry
RfI
RfI
In(C2H5)3
ml (mmol)
22 Hz, In(CH2CH2CF2CF3)2I; d 3.1 ppm,
s
(broad), In(CH2CH2 ´
ml (mmol)
CF2CF3)2I.
1
2
3
4
5
6
7
8
9
C6F5I
0.67 (5.0)
0.15 (1.1)
0.30 (2.1)
0.21 (1.5)
1.23 g (5.0)
1.84 g (7.5)
3.07 g (12.5)
0.72 (5.0)
0.86 (5.0)
1.08 (5.0)
0.80 (5.0)
0.16 (1.0)
0.16 (1.0)
0.08 (0.5)
0.80 (5.0)
0.40 (2.5)
0.40 (2.5)
0.80 (5.0)
0.80 (5.0)
0.80 (5.0)
MS (20 eV, 60 °C): 409 (28.0%, [In(CH2CH2CF2CF3)2]+); 389 (18.9%,
i-C3F7I
i-C3F7I
i-C3F7I
C2F5I
C2F5I
C2F5I
n-C3F7I
n-C4F9I
n-C6F13
[In(CH2CH2CF2CF3)I]+);
297
(12.6%,
?),
291
(20.4%,
[In(C2H5)(CH2CH2CF2CF3)]+); 271 (7.0%, [InC6H8F4]+); 242 (9.8%,
[InI]+); 115 (79.1%, [In]+); 109 (14.8%, [C4H4F3]+); 79 (98.2%,
[C3H5F2]+); 59 (39.6%, ?); 51 (24.6%, [CHF2]+); 43 (30.8%, [C3H7]+); 29
(67.5%, [C2H5]+); 28 (100%, [C2H4]+ or [N2]+).
Entries 8±10: Warming the reaction mixtures overnight gave
10
I
colourless solutions covering
a
white precipitate of
In(C2H5)2F. After distilling off all volatile compounds at
room temperature in vacuo, oily liquids remained showing
signals in the same region as described for the reactions in
the presence of N(C2H5)3. All samples were impured by
further derivatives as well as by RfH (Rf = C4F9, C6F13) and
RfI (Rf = C6F13).
Entry 1. The reaction in n-hexane was incomplete even after
7 days of stirring at ambient temperature. A white solid had
precipitated, which was identified to be In(C2H5)2F on the
basis of its mass spectrum. After distilling off n-hexane,
C6F5I and C6F5H in vacuo, an oily liquid remained. Dissolu-
tion in n-pentane again effected the precipitation of
In(C2H5)2F. The 19F-NMR spectrum of the solution showed
the resonances of In(C2H5)2(C6F5) and C6F5H in an integra-
tive ratio of about 2 : 1.
Acknowledgement. The generous support of this work by
Prof. Dr. D. Naumann is gratefully acknowledged.
The reaction without any solvent proceeded very
quickly. After stirring overnight at room temperature 19F-
NMR spectroscopic evidence was found for three In(C6F5)-
derivatives and C6F5I (integrative ratio In-deriva-
tives : C6F5I ≈ 3 : 2).
Entries 2±4: Warming the reaction mixtures from ±78 °C
to ambient temperature effected the precipitation of
In(C2H5)2F. All volatile components were condensed in va-
cuo. The 19F-NMR spectrum showed besides the resonances
of i-C3F7I, i-C3F7H and traces of hexafluoropropene a doub-
let of multiplets at ±74.8 ppm and a multiplet at ±182.4 ppm.
On the basis of mass spectrometric data of the condensate
(20 eV, 30 °C; 324 (16.2%, [(CF3)2CFCH2CH2I]+) these reso-
nances were assigned to 1-iodo-3-trifluoromethyl-3,4,4,4-te-
trafluorobutane.
References
[1] H. Lange, D. Naumann, J. Fluorine Chem. 1984, 26, 435.
[2] H. Lange, D. Naumann, J. Fluorine Chem. 1984, 26, 1.
[3] D. Naumann, K. Glinka, W. Tyrra, Z. Anorg. Allg.
Chem. 1991, 594, 95.
[4] R. Eujen, B. Hoge, J. Organomet. Chem. 1995, 503, C 51.
[5] V. Padelidakis, Diplomarbeit, UniversitaÈt zu KoÈln, 1991.
[6] D. Naumann, G. Klein, Z. Anorg. Allg. Chem. 1987,
550, 162.
[7] T. N. Bell, B. J. Pullman, B. O. West, Aust. J. Chem.
1963, 16, 636.
[8] H. Schumann,
H. Hemling, F. H. GoÈrlitz, J. Organomet. Chem. 1994,
479, 171.
[9] B. NeumuÈller, F. Gahlmann, J. Organomet. Chem. 1991,
414, 271.
[10] B. NeumuÈller, F. Gahlmann, M. SchaÈfer, J. Organomet.
Chem. 1992, 440, 263.
[11] Z.-H. Choi, W. Tyrra, unpublished results.
[12] I. J. McNaught, A. D. E. Pullin, Aust. J. Chem. 1974, 27,
1009.
[13] N. F. Cheetham, I. J. McNaught, A. D. E. Pullin, Aust. J.
Chem. 1974, 27, 973.
[14] N. F. Cheetham, I. J. McNaught, A. D. E. Pullin, Aust. J.
Chem. 1974, 27, 987.
[15] M. Chanon, M. L. Tobe, Angew. Chem. 1982, 94, 27.
[16] M. Julliard, M. Chanon, Chem. Rev. 1983, 83, 425.
[17] T. Maeda, H. Tada, K. Yasuda, R. Okawara, J. Organo-
met. Chem. 1971, 27, 13.
[18] Z.-H. Choi, Dissertation, UniversitaÈt zu KoÈln, 1996.
[19] T. Umemoto, Y. Gotoh, Bull. Chem. Soc. Jpn. 1987,
60, 3307.
[20] T. Umemoto, Y. Gotoh, Bull. Chem. Soc. Jpn. 1986, 59, 439.
[21] D. Naumann, M. Finke, H. Lange, W. Dukat, W. Tyrra,
J. Fluorine Chem. 1992, 56, 215.
[22] J. Emsley, The Elements, 2nd Ed., Clarendon, Oxford
(1991) p. 91.
T. D. Seuû,
O. Just,
R. Weimann,
The 19F-NMR-spectrum of the oil obtained after filtration
and condensation showed the resonances of In(C2H5)2(i-C3F7)
(integral 4), i-C3F7H (integral 3) and i-C3F7CH2CH2I (inte-
gral 3). Further working up was unsuccessful. However, mass
spectrometric studies during working up procedures gave evi-
dence for In(C2H5)2I formed as one of the major products.
Entries 5±7: (exemplary for entry 5 without solvent). The
mixture was diluted with CH2Cl2. The 19F-NMR-spectrum
gave evidence for three C2F5-groups directly bond to indium
and one with
a C2F5-group bond to a CH2-group
(3J(19F±1H) = 18 ± 1 Hz). The precipitate was collected and
identified as In(C2H5)2F.
Dichloromethane and all volatile compounds were con-
densed in vacuo. The resulting colourless solid was dissolved
in n-pentane. 19F-NMR spectrum showed the resonances of
two compounds in a ratio of 4 : 1.
One of the derivatives (probably that with a C2F5-group
directly bond to indium) decomposed during aqueous work-
ing up. Extraction of the aqueous mixture with diethylether
gave a white solid after distillation of (C2H5)2O that was
analyzed by multinuclear magnetic resonance spectroscopy
and mass spectrometry.
[23] D. D. Perrin, W. L. F. Armarego, Purification of Labora-
tory Chemicals, 3rd Edn., Pergamon, Oxford, New
York, Seoul, Tokyo (1988).
[24] G. Brauer, Handbuch der praÈparativen anorganischen
Chemie, Bd. II, Ferd. Enke, Stuttgart (1978), S. 863.
[25] W. Steinkopf, J. MuÈller, Chem. Ber. 1921, 54, 841.
[26] W. Tyrra, unpublished results.
NMR data of In(CH2CH2CF2CF3)2I in C6D6
19F: d(CF3) ±85.4 ppm, m; d(CF2) ±121.0 ppm, t, 3J(19F±1H) = 18.0 Hz.
1H: d 1.9 ppm, tt, 3J(19F±1H) = 18.0 Hz, 3J(1H±1H) = 8.0 Hz, In(CH2 ´
CH2CF2CF3)2I; d 0.4 ppm, t, 3J(1H±1H) = 8.0 Hz, In(CH2CH2CF2CF3)2I.