Competing reaction pathways of 3,3,3-trifluoropropene at rhodium hydrido, silyl and germyl complexes: C-F bond activation: Versus hydrogermylation

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Competing reaction pathways of 3,3,3-

triﬂuoropropene at rhodium hydrido, silyl and

germyl complexes: C–F bond activation versus

hydrogermylation†

Cite this: DOI: 10.1039/c6dt03027k

Theresia Ahrens, Michael Teltewskoi, Mike Ahrens, Thomas Braun* and

Reik Laubenstein

The reaction of the silyl complex [Rh{Si(OEt)₃}(PEt₃)₃] (1) with 3,3,3-triﬂuoropropene aﬀorded the rhodium

complex [Rh(CH₂CHCF₃){Si(OEt)₃}(PEt₃)₂] (2) which features a bonded ﬂuorinated oleﬁn. In contrast the

rhodium hydrido complex [Rh(H)(PEt₃)₃] (3) yielded on treatment with 3,3,3-triﬂuoropropene in the pres-

ence of a base the ﬂuorido complex [Rh(F)(PEt₃)₃] (4) together with 1,1-diﬂuoro-1-propene by C–F bond

activation. At low temperature the intermediate fac-[Rh(H)(CH₂CHCF₃)(PEt₃)₃] (5) was detected by NMR

spectroscopy. The germyl complex [Rh(GePh₃)(PEt₃)₃] (6) reacted also with 3,3,3-triﬂuoropropene by C–F

bond activation aﬀording again the ﬂuorido complex [Rh(F)(PEt₃)₃] (4) as well as the (3,3-diﬂuoroallyl)-

triphenylgermane 7. The catalytic hydrogermylation of 3,3,3-triﬂuoropropene in the presence of various

germanium hydrides under mild conditions was developed by employing complex 6 as a catalyst. The

molecular structures of both germane derivatives (3,3-diﬂuoroallyl)triphenylgermane 7 and 1,1,1-triﬂuoro-

propane-3-triphenylgermane 8 were determined by X-ray crystallography.

Received 30th July 2016,

Accepted 6th October 2016

DOI: 10.1039/c6dt03027k

www.rsc.org/dalton

for a catalytic C–F bond transformation of hexafluoropropene

in the presence of HBpin (pin = pinacolato) or tertiary silanes

Introduction

Fluoroorganic compounds receive a lot of attention due to to aﬀord fluoroalkyldioxaborolanes or 3,3,3-trifluoropropyl-

their broad field of applications as potential building blocks silanes, respectively.^78,79Note that not in any of these cases a

in pharmaceuticals, agrochemicals or in material science.^1–6C–F activation and functionalization of the trifluoromethyl

Therefore, it is not surprising that there is a continuing group was observed. However, Rieger et al. recently reported

demand for the development of new routes to access fluori- the catalytic activation of 3,3,3-trifluoropropene by cationic

nated entities. The selective transition-metal mediated C–F group IV metallocenes in the presence of an excess of triiso-

bond activation represents a unique way to generate novel butylaluminum yielding in benzene 3,3-(difluoroallyl)-benzene

structural motifs.^7–34Whereas a lot of stoichiometric or cata- and 1,1-difluoro-5-methyl-hex-1-ene.⁸³Herein, we report on the

lytic C–F bond derivatization reactions of fluorinated reactivity of 3,3,3-trifloropropene with [Rh{Si(OEt)₃}(PEt₃)₃] (1),

aromatics were reported,^35–46examples for fluorinated alkenes [Rh(H)(PEt₃)₃] (3) and [Rh(GePh₃)(PEt₃)₃] (6). The observed

are comparatively limited.^47–79In most of the cases the reaction routes involve coordination at the metal centre, hydro-

conversions include C–C coupling^{48–56,58–60}or hydro- defluorination, C–F bond activation and concomitant germy-

defluorination^47,60–75reactions.^31,32,80The replacement of fluo- lation, or catalytic hydrogermylation reactions.

rine in poly- or perfluorinated molecules by a new functional

group in order to obtain a higher valuable fluorinated building

block still remains rare and challenging.^{18,27,80–82}In previous

work we demonstrated that the rhodium complexes

Results and discussion

[Rh(H)(PEt₃)₃] (3) or [Rh{(Z)-CFvCF(CF₃)}(PEt₃)₃] are suitable

Treatment of the rhodium(I) silyl complex [Rh{Si(OEt)₃}(PEt₃)₃]

(1) with 3,3,3-trifluoropropene aﬀorded the alkene complex

[Rh(CH₂CHCF₃){Si(OEt)₃}(PEt₃)₂] (2) by coordination of the

fluorinated olefin and replacement of one phosphine ligand

(Scheme 1). Complex 2 was only characterized in solution,

because it is only stable in solution for about 1.5 hours. After

this time the NMR spectroscopic data of the reaction solution

Humboldt-Universität zu Berlin, Department of Chemistry, Brook-Taylor-Straße 2,

D-12489 Berlin, Germany. E-mail: thomas.braun@chemie.hu-berlin.de

†Electronic supplementary information (ESI) available. CCDC 1496565 and

1496566. For ESI and crystallographic data in CIF or other electronic format see

DOI: 10.1039/c6dt03027k

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group either orientated towards the silyl ligand or the vacant

coordination site (see also ESI†).

The calculations did not converge in any conceivable tri-

gonal bipyramidal arrangements of the ligands. The isomer

with the lowest energy (2a) in the gas phase exhibits an anti

conformation of the silyl and CF₃group as depicted in Fig. 1.

The Rh–C [2.132 and 2.113 Å] and the C–C(CF₃) [1.442 Å] bond

distances of 2a indicate a considerable contribution of a meso-

meric metallacyclopropane structure, although the ¹J_Rh,Pcoup-

ling constants are in the typical range for rhodium(^I) com-

plexes (see below).^62,85,87,88The C–C(CF₃) bond distance in the

DFT-optimized structure of 3,3,3-trifluoropropene is 1.322 Å

(see also ESI†) and rather short when compared to the

data of 2a. However, note also that the complexes

[Rh(C₂H₄)(H₂O){MeC(CH₂PPh₂)₃}] [C–C: 1.406(11) Å] and

[Rh(C₂H₄)(η⁵:η¹-C₅H₄(CH₂)₂PPh₂)] [C–C: 1.402(9) Å] were

assigned as Rh(^I) complexes based on their molecular struc-

tures in the solid state.^89,90

When the rhodium hydrido complex [Rh(H)(PEt₃)₃] (3) in

benzene was treated with 3,3,3-trifluoropropene in the pres-

ence of NEt₃and Cs₂CO₃a diﬀerent reaction pathway was

observed (Schemes 1 and 2). The base combination is used for

trapping traces of HF, whereas the amine is a phase-transfer

agent. At room temperature the reaction led to the activation

of the C–F bond of the trifluoromethyl group of the fluorinated

olefin to aﬀord the fluorido complex [Rh(F)(PEt₃)₃] (4) as well

Scheme 1 Reaction of 3,3,3-triﬂuoropropene with rhodium(I)

complexes.

reveal the formation of the starting compound 1 in addition to as 1,1-difluoro-1-propene.^63,91When the reaction was carried

several unidentified rhodium species.^62,64,84However, when out without the presence of a base, the formation of the litera-

the solvent, the excess of 3,3,3-trifluoropropene as well as the ture known rhodium bifluoride complex [Rh(FHF)(PEt₃)₃] was

phosphine were removed under vacuum immediately after also observed as

a

minor product in

a

ratio of

treatment of 1 with the fluorinated olefin, the formation of the 4 : [Rh(FHF)(PEt₃)₃] of 3 : 1.⁸⁴The formation of 4 and 1,1-

rhodium fluorido complex [Rh(F)(PEt₃)₃] (4) (ratio 2 : 4 = 4 : 1) difluoro-1-propene from 3 and 3,3,3-trifluoropropene was also

was observed. The ³¹P{¹H} NMR spectrum of 2 depicts a monitored by NMR spectroscopy at low temperature

doublet of doublet of quartets at δ = 20.5 ppm (¹J_Rh,P= 135, (Scheme 2). The studies revealed the initial generation of

4

²J_P,P= 29 and J_P,F= 19 Hz) and a doublet of doublets at δ = fac-[Rh(H)(CH₂CHCF₃)(PEt₃)₃] (5) at 203 K. The ³¹P{¹H} NMR

2

19.3 ppm (¹J_Rh,P= 137, J_P,P= 29 Hz) with an integral ratio of

1 : 1 for the two inequivalent phosphine ligands. The former

signal can presumably be assigned to the phosphorus atom in

the trans-position to the CHCF₃group, which also indicates a

restricted rotation of the fluorinated olefin at the metal centre

on the NMR time-scale. The ¹⁹F NMR spectrum exhibits a mul-

tiplet signal at δ = −53.4 ppm which can be assigned to the

CF₃group. In a ¹H decoupling experiment it simplifies to a

doublet with a fluorine phosphorus coupling constant of

⁴J_P,F= 19 Hz. The ¹H, ²⁹Si HMBC NMR spectrum shows a cross

peak at δ = −49 ppm in the ²⁹Si domain which correlates to the

CH₂and CH₃groups of the ethoxy moieties as well as to the

rhodium bonded CH₂group of the η²-coordinated trifluoro-

propenyl ligand. The chemical shift diﬀers when compared to

structurally related rhodium silyl complexes bearing no fluori-

nated ligand such as [Rh{Si(OR)₃}(PEt₃)₃] [R = Et (δ =

−11 ppm); Me (δ = −8 ppm)] or [Rh{Si(OEt)₃}(CO)(PEt₃)₂] (δ =

−10 ppm).^85,86DFT calculations were run on conceivable

rotational isomers of 2. The structures exhibit a distorted

Fig. 1 Part of DFT-optimized structure of the isomer of

[Rh(CH₂CHCF₃){Si(OEt)₃}(PEt₃)₂] (2a) with the lowest energy. The ethyl

square pyramidal coordination of the ligands at the metal

groups of the phosphine ligands and the silyl ligand have been omitted

center with the silyl ligand at the apical position and the CF₃for clarity.

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2

1

position (²J_Pcis,H≈ J_Pcis,H= 20, J_Rh,H= 10 Hz). In a ³¹P NMR

decoupling experiment the signal simplifies to a doublet

confirming the ¹J_H,Rhcoupling constant.

As above for complex 2, conceivable rotational isomers of 5

were calculated by DFT. The optimized structures diﬀer in the

orientation of the trifluoromethyl group with respect to the

hydrido ligand. The computed structure where the trifluoro-

methyl group points in the same direction as the hydrido

ligand seems to be more stable than a anti-configuration

(Fig. 2). The C–C(CF₃) bond distance with 1.437 Å in 5a is

again noticeable longer when compared to data of the DFT-

optimized structure of 3,3,3-trifluoropropene (1.322 Å, see

ESI†) but comparable to the distance in the silyl complex

[Rh(CH₂CHCF₃){Si(OEt)₃}(PEt₃)₂] (2a).

Treatment of the rhodium germyl complex [Rh(GePh₃)-

(PEt₃)₃] (6) with 3,3,3-trifluoropropene also gave the fluorido

complex 4 by C–F activation as well as the germylated difluoro-

alkene 7 (Scheme 1).⁹⁷Remarkably, a rare derivatization of the

fluorinated substrate was achieved which yielded a new fluori-

Scheme 2 C–F bond activation of 3,3,3-triﬂuoropropene at [Rh(H)-

(PEt₃)₃] (3).

spectrum of the reaction solution shows three signals for the nated building block. Due to the similar solubility properties

three inequivalent phosphine ligands at δ = 18.7, 16.6 and of complex 4 and the (3,3-difluoroallyl)triphenylgermane 7 in

4.6 ppm an integral ratio of 1 : 1 : 1. The signal patterns are in various solvents such as toluene, benzene, pentane or Et₂O, it

accordance with a fac-configuration for 5. The doublet of was not possible to isolate the olefin.

doublet of doublet of doublet of quartets at δ = 18.7 ppm can

In the ¹⁹F NMR spectrum of 7 two resonance signals were

be assigned to the phosphine ligand in the trans-position to observed for the CF₂unit. A doublet at δ = −90.2 ppm and a

the CHCF₃moiety of the fluorinated olefin. The observed split- doublet of doublets at δ = −92.6 ppm showing a characteristic

ting pattern is due to the coupling to the rhodium atom (¹J_Rh,Pgeminal fluorine–fluorine coupling constant of 50 Hz.^91,98–101

= 132 Hz), the coupling to the phosphorous atoms of the other The latter signal can be assigned to the fluorine atom in the

2

3

two phosphine ligands (²J_P,P= 33 and J_P,P= 27 Hz) as well as trans-position to the vinylic proton with a J_F,Hcoupling con-

to coupling to the fluorine atoms of the trifluoromethyl group stant of 25 Hz.^91,101–103The signal for the vinylic proton

(⁴J_P,F= 19 Hz). The inequivalence of the two phosphorus appears in the ¹H NMR spectrum as a doublet of doublet of

centers cis to the hydride ligand is consistent with restricted triplets due to coupling to both fluorine atoms (³J_H,Fcis= 2.4 Hz)

rotation of the olefin on the NMR time-scale. For the phospho- as well as to the coupling to the CH₂group. In the ¹³C{¹H}

rous atom in trans-position to the CH₂-group of the olefin a NMR spectrum three resonance signals for the CF₂vCHCH₂-

doublet of doublet of doublets at δ = 16.6 ppm with a compar- moiety were detected. The doublet of doublets at

δ =

1

able rhodium–phosphorous coupling constant of J_Rh,P

=

156.6 ppm can be assigned to the CF₂group with typical

130 Hz and phosphorous–phosphorous coupling constants of

2

²J_P,P= 33 and J_P,P= 30 Hz was observed. In contrast, the reson-

ance signal at δ = 4.6 ppm shows a comparable splitting pattern

and similar phosphorous–phosphorous coupling constants but a

noticeable smaller rhodium–phosphorous coupling constant

(¹J_Rh,P= 90 Hz), and can therefore be assigned to the phos-

phorus atom in the trans-position to the hydrido ligand. The

smaller coupling may be attributed to the large trans-influence

4

of the hydrido ligand.^92–95The J_P,F= 19 Hz coupling is also

1

observed in a H decoupled ¹⁹F NMR spectrum, that shows a

resonance signal for the CF₃group at δ = −54.8 ppm which

appears as a doublet. The ¹H NMR spectrum reveals three reso-

nance signals at δ = 2.65, 2.07 and 1.49 ppm for the hydrogen

atoms of the coordinated 3,3,3-trifluoropropene, which is in

accordance with the data of the previously reported nickel

complex [Ni(CO)(C₃H₃F₃)(I^tBu)] (I^tBu = N,N-di(tert-butyl)imida-

zol-2-ylidene).⁹⁶For the metal-bound hydrogen atom the spec-

trum depicts an apparent doublet of triplets of doublets at δ =

Fig. 2 Part of the DFT-optimized structure of the isomer of

fac-[Rh(H)(CH₂CHCF₃)(PEt₃)₃] (5a) with the lowest energy. The ethyl

−14.36 ppm revealing a large phosphorus–hydrogen coupling

2

of J_Ptrans,H= 165 Hz to a phosphine ligand in the trans- groups of the phosphine ligands have been omitted for clarity.

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¹J_C,Fcoupling constants of 286.1 and 283.0 Hz. The CH unit

also appears as a doublet of doublets at δ = 76.0 ppm but with

smaller carbon–fluorine coupling constants (²J_C,F= 24.9 and

21.0 Hz). For the CH₂-group a doublet was observed with a C,F

coupling (³J_C,F= 2.8 Hz). The assignment of the signals was

1

supported by a H, ¹³C HMBC NMR spectrum as well as a ¹⁹F,

¹³C HMBC NMR spectrum (Fig. 3). Suitable crystals for an ana-

lysis by X-ray crystallography of the difluoroalkene 7 were

obtained on one occasion from the reaction mixture in

n-hexane at 243 K. The molecular structure in the solid state is

illustrated in Fig. 4 and selected bond lengths and angles are

summarized in Table 1. Compound 7 crystalizes in the triclinic

ˉ

space group P1. The C2–C3 bond distance is with 1.291(2) Å

rather short compared to the respective separations in other

difluoroalkenes like CF₂vCHR [R = H 1.305(1) Å); R = F 1.307

Fig. 4 Molecular structure of 7 (ORTEP diagram). Ellipsoids are drawn

(1) Å; R = CFvCF₂1.318 (3) Å; R = CHvCF₂1.321(1) at 50% probability level. C–H hydrogen atoms of the phenyl groups

Å]^101,104,105but is in the same range as the ones for germylated

were omitted for clarity.

fluoroolefins such as Ph₃GeCFvCF₂(1.230(8) Å),⁹⁸

Ph₃GeCClvCF₂(1.300(8) Å),⁹⁹Ph₃GeCFvCFCF₃(1.321(8)

Å).¹⁰⁶The F1–C3–F2 angle is with 107.45(15)° noticeable

Table 1 Selected bond lengths [Å] and angles [°] in 7

smaller than 120° but in good accordance to the data for the

previously mentioned difluoroalkenes.¹⁰⁵The torsion angle

Lengths [Å]

Ge1–C1

C1–C2

1.9764(16)

1.496(2)

1.291(2)

C3–F1

C3–F2

1.327(2)

1.316(2)

Ge1–C1–C2–C3 is 115.67°.

Mechanistically it is likely that after a precoordination of

the 3,3,3-trifluoropropene at the rhodium(^I) complexes 3 or 6

an insertion of the fluorinated olefin into the metal–E (E = H,

Ge) bond occurs which is followed by an β-fluorine elimination

yielding the fluorido complex and the difluoroalkene

(Scheme 3). Presumably this involves a phosphine dissociation

prior to the β-fluorine elimination followed by an association

of PEt₃. Jones et al. and Lentz and co-workers also described

β-fluorine elimination reactions at low valent early transition-

metal complexes such as [Cp*₂Zr(H)(X)] (X = H, F) or

[Cp₂Ti(F)₂].^{63,65,70,72,73,107}

C2–C3

Angles [°]

Ge1–C1–C2

C1–C2–C3

C2–C3–F1

115.64(12)

125.63(17)

126.21(17)

C2–C3–F2

F1–C3–F2

126.33(17)

107.45(15)

In general, examples for the transition-metal mediated acti-

vation of fluorinated alkyl groups are rare, but as mentioned

above, most impart alkyl groups at fluorinated olefins or aro-

matics and result in the formation of cross-coupling or hydro-

defluorination products.^{51,53,59,63,73,108–117}Note that by

Fig. 3 ¹⁹F, ¹³C HMBC NMR spectrum (282.4 MHz/75.4 MHz, C₆D₆) of (3,3-diﬂuoroallyl)triphenylgermane 7.

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Scheme 3 Possible mechanisms for the C–F bond activation reaction and hydrogermylation of 3,3,3-triﬂuoropropene.

employing various Lewis acids the cleavage of tertiary C–F and 1.56 ppm. The signals can be simulated as AA′ and BB′

bonds can also be induced.^118–135As mentioned above C–F parts of an AA′BB′X₃spin system (Fig. 5).¹³⁶

bond functionalizations to access new fluorinated building

Suitable crystals for a X-ray crystallography analysis of the

blocks include C–C coupling, hydrodefluorination, silylation hydrogermylation product 8 were obtained after recrystalliza-

and borylation reactions.⁸⁰However, a catalytic conversion of tion in n-hexane by slow evaporation of the solvent from a satu-

3,3,3-trifluoropropene with HGePh₃in the presence of the rated heptane solution at room temperature. The molecular

germyl complex 6 did not lead to (3,3-difluoroallyl)triphenyl- structure of the germane in the solid state is illustrated in

germane 7. Instead, complex 6 catalyzes a selective hydro- Fig. 6 and selected bond lengths and angles are summarized

germylation of 3,3,3-trifluoropropene under mild conditions in Table 2. Compound 8 crystalizes in the monoclinic space

and in good yield. On using 2 mol% of 6 a full conversion of group P2₁/c. The Ge1–C3 bond distance is with 1.966(4) Å

HGePh₃was observed according to the NMR spectra after 6 h comparable to the one in the difluoroalkene 7. The C–C

at room temperature (TON 38). The 1,1,1-trifluoropropane-3- bond lengths C1–C2 [1.492(6) Å] and C2–C3 [1.519(6) Å]

triphenylgermane 8 was isolated with a yield of 73% corres- are in a typical range for single bonds. The torsion angle

ponding to a TON of 35 based on the amount of triphenyl-

germane that was employed. Note that the blank test in

absence of 6 revealed the formation of 8 in traces (yield 4.6%)

after 6 h at room temperature. The germane 8 was character-

ized by NMR spectroscopy, X-ray crystallography analysis and

1

elemental analysis (Scheme 4). The H NMR spectrum shows

two signals of higher order for the methylene groups at 2.08

Fig. 5 Part of the ¹H NMR (500.1 MHz, [D₆]benzene) spectrum of

Ph₃GeCH₂CH₂CF₃(8); simulated (bottom) observed (top) using the fol-

lowing coupling constants (Hz): ²J(H^a,H^a’) = 14.98, ³J(H^a,H^b) = 13.67,

Scheme 4 Rhodium-catalyzed

triﬂuoropropene.

hydrogermylation

of

3,3,3-

³J(H^a,H^b’) = 4.38, ³J(H^a,F) = 10.69, ³J(H^a’,H^b) = 3.79, ³J(H^a’,H^b’) = 13.98,

³J(H^a’,F) = 9.89, ²J(H^b,H^b’) = 13.76, ⁴J(H^b,F) = 0.65 and ⁴J(H^b’,F) = 0.25.

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Fig. 6 Molecular structure of 8 (ORTEP diagram). Ellipsoids are drawn

at the 50% probability level. C–H hydrogen atoms of the phenyl groups

were omitted for clarity.

Scheme 5 Scope of the hydrogermylation reaction with diﬀerent ger-

manium hydrides.

Table 2 Selected bond lengths [Å] and angles [°] in 8

Lengths [Å]

C1–C2

C2–C3

Ge1–C3

Angles [°]

Ge1–C3–C2

1.492(6)

1.519(6)

1.966(4)

F1–C1

F2–C1

F3–C1

1.339(5)

1.341(5)

1.343(5)

pound 6 seems to be active and this opens up pathways for

dehydrogermylation reactions and the generation of complex

3. The formation of digermanes was supported by GC-MS

measurements. Intermediate rhodium hydrido complexes

[Rh(H)(PEt₃)_n] (n = 3, 4) and tertiary germanes can thus serve

as sources for hydrogen resulting in hydrogenation reactions

of 3,3,3-trifluoropropene aﬀording 1,1,1-trifluoropropane as a

minor product.⁶²

Hydrogermylation reactions of olefins and alkynes have

been described, but in contrast to comparable silylation reac-

tions examples are limited.^137–141Hydrogermylation reactions

can also proceed via radical pathways and can be initiated by

additives, photochemically as well as thermally, but then are

often not selective.^{137,142–147}However, transition-metal

mediated hydrogermylations have also been reported.^{146,148–158}

Recently, Blanchard and co-workers established a stereo-

selective hydrogermylation of α-trifluoromethylated alkynes

and employed the germylated compounds in subsequent

cross-coupling reactions.¹⁵⁸Note that hydrosilylation reactions

of 3,3,3-trifluoropropene with HSiPh₃yielding 1,1,1-trifluoro-

propane-3-triphenylsilane were described before using [Rh(H)-

(PEt₃)₄] as a catalyst.⁷⁸

112.6(3)

C1–C2–C3

112.8(4)

C1–C2–C3–Ge1 with 176.30° exemplifies an antiperiplanar

conformation of the GePh₃group and the CF₃group. In con-

trast to the mechanism mentioned above for the C–F bond

activation of the fluorinated olefin at the germyl complex 6 a

diﬀerent reaction pathway becomes feasible in the presence of

an excess HGePh₃when the reaction is carried out under cata-

lytic conditions (Scheme 3). After the insertion of the 3,3,3-

trifluoropropene into the rhodium–germanium bond an

oxidative addition of HGePh₃which is followed by the reduc-

tive elimination of 1,1,1-trifluoropropane-3-triphenylgermane

appears to be faster than the β-fluorine elimination pathway.

To expand the scope of the hydrogermylation reaction

HGeEt₃and HGe(nBu)₃were also employed for the transform-

ation of 3,3,3-trifluoropropene into trifluoropropylgermanes

with 6 as catalyst (Scheme 5). However, the conversions were

less selective and the formation of 1,1,1-trifluoropropane as a

minor product was also observed, and for both germanes

longer reaction times are required at room temperature. At

50 °C the TONs are noticeable lower compared to the reaction

of HGePh₃. After a period of 6 h the NMR spectroscopic

Conclusions

measurements of the reaction solutions did not show any In conclusion we have reported on rhodium-mediated acti-

further growth of the signals of the products. Note that in vation reactions of 3,3,3-trifluoropropene. At [Rh{Si(OEt)₃}-

these conversions traces of 7 were also generated. For HGePh₃(PEt₃)₃] (1), [Rh(H)(PEt₃)₃] (3) or [Rh(GePh₃)(PEt₃)₃] (6) coordi-

no oxidative addition of the germane at 6 was observed by nation, hydrodefluorination, or C–F bond activation and conco-

NMR spectroscopy. However, in the case of HGeEt₃and HGe(n- mitant germylation were observed, respectively. The latter two

Bu)₃an initial oxidative addition at the Rh(I) germyl com- routes are accompanied by a double bond migration to generate

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fluoropropenes with a geminal configuration of the fluorine the generation of free PEt₃. Analytical data for [Rh(CH₂CHCF₃)

atoms, whereas the reaction of [Rh{Si(OEt)₃}(PEt₃)₃] (1) with {Si(OEt)₃}(PEt₃)₂] (2): ¹H NMR (300.1 MHz, [D₈]toluene): δ =

3

3,3,3-trifluoropropene is less selective, but there are some indi- 3.64 (q, J(H,H) = 6.7 Hz, 6H; SiOCH₂CH₃), 2.36 (m, dd in the

cations for a C–F bond cleavage. Note that the structurally ¹H{³¹P}NMR spectrum J = 9.3, J = 5.4 Hz, 1H; vCH₂), 2.04 (m,

related boryl complex [Rh(Bpin)(PEt₃)₃] does react on a stoichio- 1H; vCH₂), 1.93–1.72 (m, 12H; PCH₂CH₃), 1.42 (m, 1H; vCH),

metric scale, but the conversion is not selective and the pro- 1.07 (t, ³J(H,H) = 6.7 Hz, 9H; SiOCH₂CH₃), 1.04 (m, t in the

3

ducts were not identified. However, on a catalytic scale the C–F ¹H{³¹P}NMR spectrum, J(H,H) = 7.5 Hz, 9H; PCH₂CH₃), 0.94

bond activation reaction at 6 seems to be slower than a compet- (t, ³J(H,H) = 7.6 Hz, 9H; PCH₂CH₃) ppm. ¹⁹F NMR (282.4 MHz,

ing hydrogermylation. Therefore 6 can be employed as a catalyst [D₈]toluene): δ = −53.4 (m, d in the ¹⁹F{¹H}NMR spectrum

for hydrogermylation reactions. Comparable rhodium-catalyzed ⁴J(P,F) = 19 Hz, 3F; CF₃) ppm. ³¹P{¹H} NMR (121.5 MHz, [D₈]

hydrosilylation reactions of 3,3,3-trifluoropropene have been toluene): δ = 20.5 (ddq, ¹J(Rh,P) = 135, ²J(P,P) = 29, ⁴J(P,F) =

reported.⁷⁸In future work the germylated products might be 19 Hz, 1P), 19.3 (dd, ¹J(Rh,P) = 137 Hz, ²J(P,P) = 29 Hz, 1P)

employed in cross-coupling reactions. Note that Hoge and co- ppm. ¹H,²⁹Si HMBC NMR (300.1/59.6 MHz, [D₈]toluene)

workers recently demonstrated that various tris(pentafluoro- δ: 3.7/−49 (SiOCH₂CH₃), 2.4/−49 (vCH₂/SiOCH₂CH₃), 1.1/−49

ethyl)germanes

are

suitable

precursors

for

ionic (SiOCH₂CH₃) ppm.

compounds.^159–161

Formation of fac-[Rh(H)(CH₂CHCF₃)(PEt₃)₃] (5). 3,3,3-

Trifluoropropene was bubbled for 30 s into a solution of

[Rh(H)(PEt₃)₃] (3) (20 mg, 0.044 mmol) in [D₈]toluene (0.5 mL)

at 203 K. After five min the low-temperature NMR spectro-

scopic data revealed the quantitative the formation of

fac-[Rh(H)(CH₂CHCF₃)(PEt₃)₃] (5). Analytical data for

Experimental

General methods and instrumentations

The synthetic work was carried out with a Schlenk line or in a fac-[Rh(H)(CH₂CHCF₃)(PEt₃)₃] (5): ¹H NMR (300.1 MHz, [D₈]

glove box under an atmosphere of argon. All solvents were toluene, 218 K): δ = 2.65 (s, br; m in the ¹H{³¹P} NMR spec-

1

purified and dried by conventional methods and distilled trum, 1H; CH), 2.07 (m, d in the H{³¹P} NMR spectrum, J =

1

under an atmosphere of argon before use. [D₆]Benzene, [D₈]thf 10 Hz, 1H; CH), 1.74 (ddq, dq in the H{³¹P} NMR spectrum,

and [D₈]toluene were dried by stirring over Na/K and then ²J(H,H) = 14, J(P,H) = 8, J(H,H) = 7 Hz, 3H; PCH₂CH₃), 1.55

2

3

1

2

distilled. Triphenylgermane and 3,3,3-trifluoropropene were (ddq, dq in the H{³¹P} NMR spectrum, J(H,H) = 14, J(P,H) =

obtained from ABCR, triethylgermane and tri-n-butylgermane 8, ³J(H,H) = 7 Hz, 3H; PCH₂CH₃trans to CHCF₃), 1.46 (ddq, dq

from Alfa Aesar. All germanes were used without further purifi- in the H{³¹P} NMR spectrum, J(H,H) = 14, J(P,H) = 8, J(H,

1

2

3

cation. [Rh{Si(OEt)₃}(PEt₃)₃] (1), [Rh(H)(PEt₃)₃] (3) and H) = 7 Hz, 7H; PCH₂CH₃, PCH₂CH₃trans to the CHCF₃, CH),

1

[Rh(GePh₃)(PEt₃)₃] (6) were prepared according to the litera- 1.12 (m, 6H; PCH₂CH₃trans to RhH), 1.08 (td, t in the H{³¹P}

ture.^85,95,97,162The NMR spectra were acquired on a Bruker NMR spectrum, ³J(P,H) = 13, ³J(H,H) = 7 Hz, 9H; PCH₂CH₃),

DPX 300, Bruker Avance 300 or Bruker Avance 400 spectro- 0.98 (td, t in the ¹H{³¹P} NMR spectrum, ³J(P,H) = 13,

meter. The ¹H and ¹³C NMR chemical shifts were referenced to ³J(H,H) = 7 Hz, 9H; PCH₂CH₃trans to CHCF₃), 0.81 (td, t in the

residual [D₅]benzene at δ = 7.15 ppm, [D₇]thf at δ = 1.73 ppm ¹H{³¹P} NMR spectrum, ³J(P,H) = 13, ³J(H,H) = 7 Hz, 9H;

or [D₇]toluene at δ = 2.09 ppm. The ¹⁹F NMR spectra were refer- PCH₂CH₃trans to RhH), −14.36 (dtd, d in the ¹H{³¹P} NMR

2

1

enced to external CFCl₃at δ = 0.0 ppm. The ³¹P{¹H} NMR spectrum, J(P_trans,H) = 165, J(P_cis,H) = J(P_cis,H) = 20, J(Rh,

spectra were referenced externally to 85% H₃PO₄at δ = H) = 10 Hz, 1H; RhH) ppm. The assignment of the signals is

0.0 ppm. ²⁹Si{¹H} NMR spectra were referenced externally to supported by a ¹H, ¹H COSY NMR spectrum and a ¹H,

Si(CH₃)₄at δ = 0.0 ppm. Microanalyses were measured with a ³¹P HMBC NMR spectrum. Note the overlap of the signal for

HEKAtech Euro EA 3000 elemental analyzer. GC MS analyses the hydrogen atom of the CHCF₃with a signal of the protons

were performed with a Shimadzu GCMS-QP2010SE equipped of the phosphine ligand. ¹⁹F NMR (282.4 MHz, [D₈]toluene,

with a Shimadzu Rtx®-5MS column. The yield of the hydroger- 203 K): δ = −54.8 (m, d in the ¹⁹F{¹H} NMR spectrum, J(P,F) =

mylation products 8, 9 and 10 were determined from ¹⁹F NMR 19 Hz; CF₃) ppm. ³¹P{¹H} NMR (161.9 MHz, [D₈]toluene,

spectra by integration of product resonances versus the exter- 203 K): δ = 18.7 (dddq, ¹J(Rh,P) = 132, ²J(P,P) = 33, ²J(P,P) = 27,

nal standard C₆H₅CF₃and are based on the amount of HGeR₃⁴J(P,F) = 19 Hz, 1P; P trans to CHCF₃), 16.6 (ddd, ¹J(Rh,P) =

2

1

(Et, nBu, Ph) that was employed [TON

RGeCH₂CH₂CF₃(R = Et, nBu, Ph) (mol)/amount of rhodium ²J(P,P) = 30, ²J(P,P) = 27 Hz, 1P; P trans to RhH) ppm.

complex (mol)]. Reaction of 3,3,3-trifluoropropene with [Rh(H)(PEt₃)₃] (3). To

= amount of 130, J(P,P) = 33, J(P,P) = 30 Hz, 1P), 4.6 (ddd, J(Rh,P) = 90,

Formation of [Rh(CH₂CHCF₃){Si(OEt)₃}(PEt₃)₂] (2). A solu- a solution of [Rh(H)(PEt₃)₃] (3) (150 mg, 0.327 mmol) in

tion of [Rh{Si(OEt)₃}(PEt₃)₃] (1) (25 mg, 53 µmol) in benzene (10 mL) NEt₃(140 µL, 1.006 mmol) and Cs₂CO₃

[D₈]toluene (0.5 mL) in a Young NMR tube equipped with a (330 mg, 1.013 mmol) were added. 3,3,3-Trifluoropropene was

PFA inliner was cooled to 77 K, degassed in vacuo, and pressur- then bubbled for 30 s into the reaction solution. The NMR

ized with 3,3,3-trifluoropropene to 1 atm. After warming up to spectroscopic data of the reaction mixture reveals the for-

room temperature the NMR spectroscopic data of the reaction mation of 1,1-difluoropropene and [Rh(F)(PEt₃)₃] (4). All vola-

mixture revealed the complete conversion of 1 into 2 as well as tiles were removed in vacuum and the residue was extracted

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with n-hexane (3 × 3 mL). The solvent was removed from the reveal the complete conversion of HGePh₃as well as the for-

extract in vacuum. The NMR spectroscopic data of the residue mation of (67%; TON 33). Analytical data for

8

=

reveals the formation of [Rh(F)(PEt₃)₃] (4) (90%). Complex 4 Ph₃GeCH₂CH₂CF₃(8): C₂₁H₁₉F₃Ge (401.01): calcd C, 62.90; H,

and 1,1-difluoropropene were identified by comparison of 4.78; found: C, 63.31; H, 4.86. ¹H NMR (500.1 MHz,

their analytical data with the literature.^62,64,84

[D₆]benzene): δ = 7.33 (m, 6H; Ph), 7.14–7.09 (m, 9H; Ph) 2.08

Reaction of 3,3,3-trifluoropropene with [Rh(GePh₃)(PEt₃)₃] (m, ²J(H^a,H^a′) = 14.98, ³J(H^a,H^b) = 13.67, ³J(H^a,H^b′) = 4.38,

3

(6). In a Young NMR tube [Rh(GePh₃)(PEt₃)₃] (6) (17 mg, ³J(H^a,F) = 10.69, J(H^a′,H^b) = 3.79, J(H^a′,H^b′) = 13.98, J(H^a′,F)

22.3 µmol) was dissolved in [D₈]toluene (0.3 mL). The solution = 9.89 Hz, 2H; CH₂), 1.56 (m, ³J(H^a,H^b) = 13.67, ³J(H^a,H^b′) =

was cooled to 77 K, degassed in vacuo, and pressurized with 4.38, J(H^a′,H^b) = 3.79, ³J(H^a′,H^b′) = 13.98, ⁴J(H^b,F) = 0.65

3,3,3-trifluoropropene to 1 atm. After warming up to room ⁴J(H^b′,F) = 0.25 Hz, 2H; CH₂GePh₃) ppm. The coupling con-

temperature the NMR spectroscopic data of the reaction stants were determined by simulation with gNMR.^{136 13}C{¹H}

mixture revealed after 4 h the complete conversion of 6 into NMR (75.5 MHz, [D₈]thf): δ = 136.3 (s, Ph), 135.4 (s, Ph), 129.8

1

[Rh(F)(PEt₃)₃] (4) as well as the formation of (3,3-difluoroallyl)- (s, Ph), 129.0 (s, Ph) 128.6 (q, J(C,F) = 276 Hz; CF₃), 30.3 (q,

3

triphenylgermane 7. Complex 4 was identified by comparison ²J(C,F) = 30 Hz; CH₂), 5.9 (q, J(C,F) = 2 Hz; CH₂GePh₃) ppm,

of its analytical data with the literature.^62,64,84Analytical data the assignment of the signals is supported by a ¹⁹F,¹³C{¹H}

1

for 7: H NMR (300.1 MHz, [D₆]benzene): δ = 7.44 (m, 6H; Ph), HMBC NMR spectrum (see also ESI†). ¹⁹F NMR (282.4 MHz,

7.18 (m, 9H; Ph), 4.15 (ddt, ³J(H,F^α) = 24.7, ³J(H,H) = 8.8, ³J(H, [D₈]thf): δ = −71.2 (t, ³J(F,H) = 10 Hz, 3F; CF₃) ppm.

3

4

F^β) = 2.4 Hz, 1H; CH), 1.98 (dt, J(H,H) = 8.8, J(H,F) = 1.7 Hz,

Catalytic conversion of 3,3,3-trifluoropropene with HGeEt₃.

2H; CH₂) ppm. ¹³C{¹H} NMR (75.5 MHz, [D₈]thf): δ = 156.6 (a) In a Young NMR tube [Rh(GePh₃)(PEt₃)₃] (6) (5.5 mg,

(dd, ¹J(C,F^α) = 286.1, ¹J(C,F^β) = 283.0 Hz; CF₂), 136.8 (s, Ph), 7.22 µmol) and HGeEt₃(58 µL, 0.361 mmol) were dissolved in

135.5 (s, Ph), 129.9 (s, Ph), 129.1 (s, Ph), 76.0 (dd, ²J(C,F^β) = [D₈]toluene (0.3 mL). The solution was cooled to 77 K,

24.9, ²J(C,F^α) = 21.0 Hz; CH), 8.6 (d, ³J(C,F) = 2.8 Hz; CH₂) degassed in vacuo, and pressurized with 3,3,3-trifluoropropene

ppm, the assignment of the signals is supported by a ¹H, to 1 atm. After warming up to room temperature the reaction

¹³C HMBC NMR spectrum as well as a ¹⁹F, ¹³C{¹H} HMBC was monitored by NMR spectroscopy. After 2 d at room temp-

1

NMR spectrum. ¹⁹F NMR (282.4 MHz, [D₈]thf): δ = −90.2 (d, erature the H and ¹⁹F NMR spectroscopic data reveal the for-

²J(F,F) = 50 Hz, 1F; F^β), −92.6 (dd, ²J(F,F) = 50, ³J(F,H) = 25 Hz, mation of Et₃GeCH₂CH₂CF₃(9) (25%; TON = 12) as well as of

1F; F^α) ppm (for the labeling of the fluorine atoms see also 1,1,1-trifluoropropane (20%). Et₃GeGeEt₃was identified as a

Scheme 1).

minor product by comparison with literature data and by

Treatment of HGePh₃with 3,3,3-trifluoropropene. In a GC-MS analysis of the reaction mixtures.¹⁶³(b) In a Young

Young NMR tube HGePh₃(60 mg, 196 µmol) was dissolved in NMR tube [Rh(GePh₃)(PEt₃)₃] (6) (6.6 mg, 8.60 µmol) and

[D₈]toluene (0.4 mL). The solution was cooled to 77 K, HGeEt₃(70 µL, 0.433 mmol) were dissolved in [D₈]toluene

degassed in vacuo, and pressurized with 3,3,3-trifluoropropene (0.3 mL). The solution was cooled to 77 K, degassed in vacuo,

to 1 atm. After warming up to room temperature the reaction and pressurized with 3,3,3-trifluoropropene to 1 atm. After

solution was monitored by NMR spectroscopy. After 6 h the warming up to 323 K the reaction was monitored by NMR

¹⁹F NMR spectroscopic data revealed the formation of spectroscopy. After 6 h the ¹H and ¹⁹F NMR spectroscopic data

Ph₃GeCH₂CH₂CF₃(7) (4.6%).

reveal the formation of Et₃GeCH₂CH₂CF₃(9) (19%; TON = 12)

Catalytic conversion of 3,3,3-trifluoropropene with HGePh₃. as well as of 1,1,1-trifluoropropane (17%). Analytical data for 9:

(a) In a Young NMR tube [Rh(GePh₃)(PEt₃)₃] (6) (5.5 mg, ¹H NMR (500.1 MHz, [D₈]toluene): δ = 1.84 (m, 2H; CH₂CF₃),

7.22 µmol) was dissolved in [D₈]toluene (0.3 mL) and HGePh₃0.88 (t, ³J(H,H) = 8 Hz, 9H, GeCH₂CH₃), 0.74 (m, 2H; CH₂),

3

(110 mg, 360 µmol) was added to the solution. The solution 0.53 (q, J(H,H) = 8 Hz, 6H; GeCH₂CH₃) ppm, the assignment

1

was cooled to 77 K, degassed in vacuo, and pressurized with of the signals is supported by a H,¹³C HMBC NMR spectrum

3,3,3-trifluoropropene to 1 atm. After warming up to room as well as a ¹H,¹³C HMQC NMR spectrum. ¹³C{¹H} NMR

1

temperature the reaction was monitored by NMR spectroscopy. (128.4 MHz, [D₈]toluene): δ = 128.6 (q, J(C,F) = 277 Hz; CF₃),

After 6 h at room temperature the ¹H and ¹⁹F NMR spectro- 30.3 (q, ²J(C,F) = 30 Hz; CH₂CF₃), 8.9 (s, GeCH₂CH₃), 5.9 (q,

scopic data reveal the complete conversion of HGePh₃as well ³J(C,F) = 2 Hz; CH₂GeEt₃), 3.8 (s; GeCH₂CH₃) ppm, the assign-

as the formation of Ph₃GeCH₂CH₂CF₃(8) (77%, TON = 38). All ment of the signals is supported by a ¹H, ¹³C HMBC NMR

volatiles were removed in vacuo and the crude product was spectrum as well as a ¹⁹F, ¹³C{¹H} HMBC NMR spectrum.

recrystallized from a saturated solution in n-hexane (1.5 mL). ¹⁹F NMR (282.4 MHz, [D₈]toluene): δ = −68.9 (t, ³J(F,H) =

8 was obtained as a colorless solid. Yield 105 mg (73%; TON = 10 Hz, 3F; CF₃) ppm. GC/MS: m/z 229 [M − Et].

36). (b) In a Young NMR tube [Rh(GePh₃)(PEt₃)₃] (6) (5.5 mg,

Catalytic conversion of 3,3,3-trifluoropropene with HGe

7.22 µmol) was dissolved in [D₈]toluene (0.3 mL) and HGePh₃(nBu)₃. In a Young NMR tube [Rh(GePh₃)(PEt₃)₃] (3) (6.0 mg,

(110 mg, 360 µmol) was added to the solution. The solution 7.88 µmol) and HGe(nBu)₃(91 µL, 0.394 mmol) were dissolved

was cooled to 77 K, degassed in vacuo, and pressurized with in [D₈]toluene (0.3 mL). The solution was cooled to 77 K,

3,3,3-trifluoropropene to 1 atm. After warming up to room degassed in vacuo, and pressurized with 3,3,3-trifluoropropene

temperature the reaction was monitored by NMR spectroscopy. to 1 atm. After warming up to room temperature the reaction

After 3 h at 323 K the ¹H and ¹⁹F NMR spectroscopic data was monitored by NMR spectroscopy. After 2 d at room temp-

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1

erature the H and ¹⁹F NMR spectroscopic data reveal the for-

Table 3 Crystallographic data

mation of (nBu)₃GeCH₂CH₂CF₃(10) (25%; TON = 12) as well as

of 1,1,1-trifluoropropane (12%). (nBu)₃GeGe(nBu)₃was identi-

fied as side product by comparison with literature data and by

GC-MS analysis of the reaction mixtures.¹⁶⁴(b) In a Young

NMR tube [Rh(GePh₃)(PEt₃)₃] (3) (5.2 mg, 6.83 µmol) and

HGe(nBu)₃(80 µL, 0.340 mmol) were dissolved in [D₈]toluene

(0.3 mL). The solution was cooled to 77 K, degassed in vacuo,

and pressurized with 3,3,3-trifluoropropene to 1 atm. After

warming up to 323 K the reaction was monitored by NMR

spectroscopy. After 6 h the ¹H and ¹⁹F NMR spectroscopic data

reveal the formation of (nBu)₃GeCH₂CH₂CF₃(10) (15%; TON =

7.5) as well as of 1,1,1-trifluoropropane (10%). Analytical data

for 10: ¹H NMR (300.1 MHz, [D₈]toluene): δ = 1.91 (m, 2H;

CH₂CF₃), 1.28 (m, 12H; CH₂), 0.90 (t, 9H; CH₃), 0.80 (m, 2H;

CH₂), 0.61 (m, 6H; CH₂) ppm, the assignment of the signals is

7

8

Crystal dimensions [mm³]

Crystal colour

Empirical formula

M

0.51 × 0.14 × 0.03 0.388 × 0.053 × 0.011

Colorless

C₂₁H₁₈F₂Ge

380.94

Triclinic

P1

9.4950(4)

9.7733(4)

10.3171(4)

67.024(2)

83.103(2)

84.211(2)

873.54(6)

2

1.448

1.771

2.16 to 28.32

28 469

4346

0.0351

99.8

Colorless

C₂₁H₁₉F₃Ge

400.95

Monoclinic

P2₁/c

16.3551(13)

14.7943(10)

7.4616(6)

Crystal system

ˉ

Space group

a [Å]

b [Å]

c [Å]

α [°]

β [°]

90.874(3)

γ [°]

V [Å³]

Z

1805.2(2)

4

1.475

1.726

2.49 to 24.55

19 769

3199

0.1394

99.7

Multi-scan

1.040

D_calcd[mg m⁻³

]

μ(Mo-K_α) [mm⁻¹

θ range [°]

]

supported by a H, ¹³C HMBC NMR spectrum as well as a H,

¹³C HMQC NMR spectrum. ¹³C{¹H} NMR (75.5 MHz,

[D₆]benzene): δ = 128.0 (q, ¹J(C,F) = 277 Hz; CF₃), 29.9 (q,

²J(C,F) = 29 Hz; CH₂), 27.2 (s, CH₂), 26.5 (s, CH₂), 13.5 (s, CH₂),

11.9 (s, CH₃), 3.7 (q, ³J(C,F) = 2 Hz; CH₂) ppm, the assignment

1

Reflns. collected

Indep. reflns.

R_int

Completeness [%]

Absorption correction

GoF on F²

R₁, wR₂(all data)

R₁, wR₂(I₀> 2)

Max. diﬀ. peak/hole [e Å⁻³

Multi-scan

1.052

0.0288, 0.0657

0.0261, 0.0643

0.543/−0.392

0.0874, 0.0894

0.0487, 0.0798

0.421/−0.409

1

of the signals is supported by a H, ¹³C HMBC NMR spectrum

as well as a ¹⁹F, ¹³C{¹H} HMBC NMR spectrum. ¹⁹F NMR

(282.4 MHz, [D₈]toluene): δ = −69.0 (t, ³J(F,H) = 10 Hz, 3F; CF₃)

ppm. GC/MS: m/z 285 [M − nBu].

]

identify them as minima (no negative eigenvalues). Energies

were corrected for zero-point energy.

Structure determination

Suitable crystals for X-ray crystallography of (3,3-difluoroallyl)-

triphenylgermane 7 were obtained from the reaction mixture

of 4 and 7 of a saturated n-hexane solution at 243 K. Colorless

crystals of 1,1,1-trifluoropropane-3-triphenylgermane 8 were

obtained by slow evaporation of the solvent from a n-heptane

solution at room temperature. Data collections were performed

at 100 K with a Bruker D8 Venture area detector. The structures

were solved by intrinsic phasing (SHELXS-2013) and refined by

full matrix least-squares procedures based on F²with all

measured reflections (SHELXL-2013).^165–167The SADABS

program was used for multi-scan absorption corrections.¹⁶⁸All

non-hydrogen atoms were refined anisotropically. All hydrogen

atom positions were placed at their idealized positions and

were refined using a riding model. CCDC 1496566 [for (3,3-

difluoroallyl)triphenylgermane 7] and 1496565 (for 1,1,1-tri-

fluoropropane-3-triphenylgermane 8) contain the crystallo-

graphic data (Table 3).

Acknowledgements

We would like to acknowledge the DFG research training

group “Fluorine as

a Key Element” (T. Ahrens and

M. Teltewskoi) for financial support. M. Ahrens thanks the

“Fonds der Chemischen Industrie”.

References

1 R. E. Banks, Fluorine Chemistry at the Millennium:

Fascinated by Fluorine, Elsevier, Amsterdam, 2000.

2 T. Hiyama, Organofluorine Compounds: Chemistry and

Applications, Springer, Berlin, 2000.

3 P. Kirsch, Modern Fluoroorganic Chemistry: Synthesis,

Reactivity and Applications, Wiley-VCH Weinheim, 2004.

4 J. A. Gladysz, Handbook of Fluorous Chemistry, Wiley-VCH,

Weinheim, 2004.

5 J. P. Bégué and D. Bonnet-Delpon, Bioorganic and

Medicinal Chemistry of Fluorine, John Wiley & Sons, Inc,

Hoboken, New York, 2008.

6 Y. Zhou, J. Wang, Z. Gu, S. Wang, W. Zhu, J. L. Aceña,

V. A. Soloshonok, K. Izawa and H. Liu, Chem. Rev., 2016,

116, 422–518.

7 J. L. Kiplinger, T. G. Richmond and C. E. Osterberg, Chem.

Rev., 1994, 94, 373–431.

Computational methods

The calculations were run using the Gaussian 09 (Revision

D.01) program package¹⁶⁹and the B3LYP functional. Plausible

ligand arrangements for [Rh{Si(OEt)₃}(CH₂CHCF₃)(PEt₃)₂] (2)

and fac-[Rh(H)(CH₂CHCF₃)(PEt₃)₃] (5) were optimized and the

depicted structures (see Fig. 1 and 2 as well as the ESI†) turned

out to be the minima. The cc-pVTZ basis sets were employed

for all rhodium- and silicon-bound atoms (cc-pVDZ for all

other carbon and hydrogen atoms). Rhodium was described

on using RECPs with the associated cc-pVTZ-PP basis set.¹⁷⁰

Frequency calculations were run for all stationary points to

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8 J. Burdeniuc, B. Jedlicka and R. H. Crabtree, Chem. Ber.,

1997, 130, 145–154.

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Competing reaction pathways of 3,3,3-trifluoropropene at rhodium hydrido, silyl and germyl complexes: C-F bond activation: Versus hydrogermylation

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