Structural and conformational properties of 2-propenylgermane (allylgermane) studied by microwave and infrared spectroscopy and quantum chemical calculations

Article abstract of DOI:10.1021/jp044294c

The structural and conformational properties of allylgermane have been investigated using Stark and Fourier transform microwave spectroscopies, infrared spectroscopy, and high-level quantum chemical calculations. The parent species H₂C=CHCH₂GeH₃ was investigated by microwave spectroscopy and infrared spectroscopy, while three deuterated species, namely, H₂C=CDCH₂GeH₃, H ₂C=CHCHDGeH3, and H₂C=CHCH₂GeD₃, were studied only by infrared spectroscopy. The microwave spectra of the ground vibrational state as well as of the first excited state of the torsion vibration around the sp²-sp³ carbon-carbon bond were assigned for the ⁷⁰Ge, ⁷²Ge, and ⁷⁴Ge isotopomers of one conformer. This rotamer has an anticlinal arrangement for the C=C-C-Ge chain of atoms. The infrared spectrum of the gas in the 500-4000 cm^-1 range has been assigned. No evidence of additional rotameric forms other than anticlinal was seen in the microwave and infrared spectra. Several different high-level ab initio and density functional theory calculations have been performed. These calculations indicate that a less stable form, having a synperiplanar conformation of the C=C-C-Ge link of atoms, may coexist with the anticlinal form. The energy differences between the synperiplanar and anticlinal forms were calculated to be 5.6-9.2 kJ/mol depending on the computational procedure. The best approximation of the equilibrium structure of the anticlinal rotamer was found in the MP2/aug-cc-pVTZ calculations. The barrier to internal rotation of the germyl group was found to be 6.561(17) kJ/mol, from measurements of the splitting of microwave transitions caused by tunneling of the germyl group through its threefold barrier.

Full text of DOI:10.1021/jp044294c

3822
J. Phys. Chem. A 2005, 109, 3822-3829
Structural and Conformational Properties of 2-Propenylgermane (Allylgermane) Studied by
Microwave and Infrared Spectroscopy and Quantum Chemical Calculations
Anne Horn,† Harald Møllendal,*,† Jean Demaison,‡ Denis Petitprez,‡
Juan Ramon Aviles Moreno,‡ Abdessamad Benidar,§ and Jean-Claude Guillemin|
Department of Chemistry, UniVersity of Oslo, P.O. Box 1033 Blindern, NO-0315 Oslo, Norway,
Laboratoire de Physique des Lasers, Atomes et Mole´cules, UMR CNRS 8523, Baˆt. P5, UniVersite´ de Lille 1,
F-59655 VilleneuVe d’Ascq, France, Equipe d’Astrochimie Expe´rimentale, Laboratoire PALMS,
UMR CNRS 6627, UniVersite´ de Rennes I, Campus de Beaulieu, F-35042 France, and Laboratoire de Synthe`se
et ActiVation de Biomole´cules, UMR CNRS 6052, Institut de Chimie de Rennes, ENSCR,
F-35700 Rennes, France
ReceiVed: December 15, 2004; In Final Form: February 16, 2005
The structural and conformational properties of allylgermane have been investigated using Stark and Fourier
transform microwave spectroscopies, infrared spectroscopy, and high-level quantum chemical calculations.
The parent species H2CdCHCH2GeH3 was investigated by microwave spectroscopy and infrared spectroscopy,
while three deuterated species, namely, H2CdCDCH2GeH3, H2CdCHCHDGeH3, and H2CdCHCH2GeD3,
were studied only by infrared spectroscopy. The microwave spectra of the ground vibrational state as well as
of the first excited state of the torsion vibration around the sp2-sp3 carbon-carbon bond were assigned for
the 70Ge, 72Ge, and 74Ge isotopomers of one conformer. This rotamer has an anticlinal arrangement for the
CdCsCsGe chain of atoms. The infrared spectrum of the gas in the 500-4000 cm-1 range has been assigned.
No evidence of additional rotameric forms other than anticlinal was seen in the microwave and infrared
spectra. Several different high-level ab initio and density functional theory calculations have been performed.
These calculations indicate that a less stable form, having a synperiplanar conformation of the CdCsCsGe
link of atoms, may coexist with the anticlinal form. The energy differences between the synperiplanar and
anticlinal forms were calculated to be 5.6-9.2 kJ/mol depending on the computational procedure. The best
approximation of the equilibrium structure of the anticlinal rotamer was found in the MP2/aug-cc-pVTZ
calculations. The barrier to internal rotation of the germyl group was found to be 6.561(17) kJ/mol, from
measurements of the splitting of microwave transitions caused by tunneling of the germyl group through its
threefold barrier.
Introduction
Gas-phase studies of the conformational properties of mol-
ecules containing the germyl group are rare. This was one
motivation to conduct this first study of 2-propenylgermane
(allylgermane), H2CdCHCH2GeH3.
The literature dealing with structural, conformational, and
dynamical properties of compounds possessing the germyl
(GeH3) group is rather limited. Accurate structures are known
in some cases, for example, germane (GeH4),1,2 the germyl
halides (GeH3X, X ) F,3 Cl,4,5 Br,5,6 and I5,6), germylacetylene
(GeH3CtCsH),7 methylgermane (H3GeCH3),8 ethylgermane
(H3GeCH2CH3),9 and cyclopropylgermane (C3H5GeH3).10 Some
structural information is available for vinylgermane (H2Cd
CHGeH3),11 (fluoromethyl)germane (H3GeCH2F12), and (chlo-
romethyl)germane (H3GeCH2Cl).13 A review of germane and
the germyl halides has been given by Bu¨rger and Rahner.14
The barrier to internal rotation of the GeH3 group has been
determined in some cases. This threefold barrier is typically
5-7.3 kJ/mol when the germyl group is attached to a sp3-
hybridized carbon atom. Examples are H3GeCH3 (5.19),8 H3-
GeCH2F (5.81(17)),12 H3GeCH2Cl (7.28(17)),13 H3GeCH2CH3
(5.98(12)),9 and cyclopropylgermane (5.58(20) kJ/mol).10 The
barrier is generally found to be lower than for corresponding
silyl (SiH3) and methyl (CH3) containing compounds.9
Allylgermane is an allylic compound. These molecules
normally exist as a mixture of two rotamers. In the first of these,
the CdCsCsGe chain of atoms takes a synperiplanar con-
formation (dihedral angle ≈ 0°), while the second rotamer has
an anticlinal conformation (dihedral angle ≈ 120° from syn-
periplanar). These two forms of allylgermane are denoted sp
and ac, respectively, and are drawn in Figure 1, where atom
numbering is also indicated.
A variety of methods, including Stark and Fourier transform
microwave (MW) spectroscopy, advanced quantum chemical
calculations, and infrared (IR) spectroscopy, have been em-
ployed in this work to investigate a series of physical properties
of the title compound. While the parent species was studied by
MW and IR methods, three additional deuterated isotopomers,
H2CdCDCH2GeH3, H2CdCHCHDGeH3, and H2CdCHCH2-
GeD3, were investigated exclusively by IR spectroscopy to
assign vibrational modes and at the same time investigate the
conformational composition of this compound.
* Corresponding author. E-mail: harald.mollendal@kjemi.uio.no. Tel.:
+47 22 85 56 74. Fax: +47 22 85 54 41.
† University of Oslo.
The MW methods are characterized by their extremely high
resolution and specificity, making them ideal techniques for
conformational studies. IR spectroscopy is also a sensitive
‡ Universite´ de Lille 1.
§ Universite´ de Rennes 1.
| ENSCR.
10.1021/jp044294c CCC: $30.25 © 2005 American Chemical Society
Published on Web 04/08/2005

Allylgermane Properties by MW and IR Spectroscopy
J. Phys. Chem. A, Vol. 109, No. 17, 2005 3823
Figure 1. Two stable rotameric forms of allenylgermane. The C1dC2sC3sGe skeleton is synperiplanar in the sp conformer and anticlinal in the
ac conformer. Atom numbering is indicated on the sp rotamer.
method for the study of conformational composition. Modern
quantum chemical calculations are now able to provide useful
predictions of molecular properties, even in compounds contain-
ing electron-rich elements such as germanium (32 electrons).
These calculations are, therefore, a useful supplement to the
experimental work.
2-Propenyltrichlorogermane (2.2 g, 10 mmol) in tetraglyme (10
mL) was slowly added with a flex needle through the septum
for about 5 min. During and after addition, 2-propenylgermane
was distilled off in vacuo from the reaction mixture. A cold
trap (-80 °C) selectively removed less volatile products, and
2-propenylgermane was condensed in a second cold trap (-120
°C) to remove the most volatile products (mainly GeH4). After
disconnecting from the vacuum line by stopcocks, the product
was kept at low temperature (<-50 °C) before analysis.
Yield: 88% (1.03 g). 1H NMR (CDCl3): δ 1.94 (dq, 2H, 3JHH
Experimental Section
Materials. Lithium aluminum hydride, lithium aluminum
deuteride, tetraethylene glycol dimethyl ether (tetraglyme), bis-
(cyclopentadienyl)zirconium chloride deuteride (deuterated
Schwartz reagent), and 2-propenyltributylstannane were pur-
chased from Aldrich and used without further purification.
2-Propynyltriphenylstannane15 and (Z)-3-deutero-2-propenyl-
triphenylstannane16 were prepared as previously reported.
Synthesis of 2-Propenylgermanes. Allylgermane was syn-
thesized in two steps. Reaction of 2-propenyltributylstannane
with germanium tetrachloride led to the 2-propenyltrichlorog-
ermane, which was then reduced with LiAlH4 to give the
expected product. The same approach was employed to syn-
thesize the three deuterated allylgermanes using a deuterated
stannane or LiAlD4 as the reducing agent.
2-Propenyltrichlorogermane.17 To a 50-mL two-necked
flask equipped with a magnetic stirring bar and a nitrogen inlet
was introduced germanium tetrachloride (4.28 g, 20 mmol).
2-Propenyltributylstannane (6.62 g, 20 mmol) was added
dropwise at room temperature for about 5 min. The mixture
was stirred at 40 °C for 3 h. The flask was then attached to a
vacuum line equipped with a trap, which was cooled at -50
°C to condense the 2-propenyltrichlorogermane selectively. The
product was distilled by heating the reaction mixture up to 40
°C. At the end of the distillation, the trap was disconnected
from the vacuum line by stopcocks and allowed to warm to
room temperature. 2-Propenyltrichlorogermane (4.05 g, 18.4
mmol) was obtained in a 92% yield. 1H NMR (CDCl3): δ 2.90
3
3
) 7.6 Hz, JHH ) 3.1 Hz, CH2sGe), 3.61 (t, 3H, JHH ) 3.1
Hz, GeH3), 4.88 (d, 1H, 3JHHcis ) 9.8 Hz, CH(H)dC), 4.99 (d,
1H, 3JHHtrans ) 15.8 Hz, CH(H)dC), 5.91 (ddt, 1H, 3JHHtrans
)
3
3
15.8 Hz, JHHcis ) 9.8 Hz, JHH ) 7.6 Hz, CHdC). 13C NMR
1
(CDCl3): δ 14.1 (t, JCH ) 130.1 Hz, CH2sGe), 113.3 (dd,
1
1
1JCH ) 160.6 Hz, JCH ) 152.4 Hz, CH2), 136.2 (d, JCH
)
152.6 Hz, CH).
Synthesis of 1-Deutero-2-propenylgermane. 1-Deutero-2-
propenyltrichlorogermane was prepared starting from (Z)-3-
deutero-2-propenyltriphenylstannane and germanium tetrachlo-
ride using the experimental procedure reported above. The
reaction occurs via an allylic transposition and only the
1-deutero-2-propenylgermane was obtained. Yield: 71%. Iso-
topic purity: >96%. 1H NMR (CDCl3): δ 2.89 (dm, 1H, 3JHH
) 7.9 Hz, 2JHD ) 0.8 Hz, CHDsGe), 5.38 (dm, 1H, 3JHHcis
)
3
10.2 Hz, CH(H)dC), 5.38 (dm, 1H, JHHtrans ) 16.3 Hz,
CH(H)dC), 5.87 (dddt, 1H, 3JHHtrans ) 16.3 Hz, 3JHHcis ) 10.2
3
3
Hz, JHH ) 7.9 Hz, JHD ) 1.0 Hz, CHdC). 13C NMR
(CDCl3): δ 36.8 (1JCD ) 20.8 Hz), 121.6, 125.9.
1-Deutero-2-propenylgermane was prepared starting from
1-deutero-2-propenyltrichlorogermane and LiAlH4 using the
experimental procedure reported above. Yield: 88%. Isotopic
1
3
purity: >95%. H NMR (CDCl3): δ 1.94 (m, 2H, JHH ) 7.6
3
3
Hz, JHH ) 3.3 Hz, CHDsGe), 3.61 (d, 3H, JHH ) 3.3 Hz,
GeH3), 4.88 (dm, 1H, 3JHHcis ) 9.8 Hz, CH(H)dC), 4.99 (dm,
3
3
3
3
1H, JHHtrans ) 15.8 Hz, CH(H)dC), 5.91 (dddq, 1H, JHHtrans
(d, 2H, JHH ) 7.9 Hz, CH2sGe), 5.38 (d, 1H, JHHcis ) 10.2
3
3
3
3
) 15.8 Hz, JHHcis ) 9.8 Hz, JHH ) 7.6 Hz, JHD ) 1.0 Hz,
CHdC). 13C NMR (CDCl3): δ 13.8 (1JCD ) 20.1 Hz), 113.3,
136.2.
Hz, CH(H)dC), 5.38 (d, 1H, JHHtrans ) 16.3 Hz, CH(H)dC),
3
3
3
5.87 (ddt, 1H, JHHtrans ) 16.3 Hz, JHHcis ) 10.2 Hz, JHH
)
7.9 Hz, CHdC). 13C NMR (CDCl3): δ 37.0 (t, JCH ) 136.5
1
1
1
Hz, CH2sGe), 121.6 (dd, JCH ) 163.0 Hz, JCH ) 155.8 Hz,
Synthesis of 2-Deutero-2-propenylgermane. 2-Deutero-2-
propenyltriphenylstannane was first prepared as follows: To a
dried Schlenk flask protected from the light by aluminum foil
and equipped with a stirring bar were introduced under argon
the deuterated Schwartz reagent (517 mg, 2 mmol) and
tetrahydrofuran (10 mL). Propynyltriphenylstannane (624 mg,
1.6 mmol, 0.8 equiv) was then added, and this mixture was
stirred at room temperature for 1 h. Pure water (1.0 mL) was
then quickly added, and the mixture was stirred for 10 min.
Diethyl ether (20 mL) was added, and the mixture was dried
1
CH2), 125.8 (d, JCH ) 159.8 Hz, CH).
Synthesis of 2-Propenylgermane.18 Caution: Allylgermane
is pyrophoric and potentially toxic. All reactions and handling
should be carried out in a well-Ventilated hood.
The apparatus used here was similar to the one described for
the preparation of 2-propynylphosphine.19 To a 250-mL two-
necked flask were introduced the reducing agent (LiAlH4, 0.76
g, 20 mmol) and tetraglyme (50 mL). The flask was connected
to a vacuum line, immersed in a cold bath (0 °C), and degassed.

3824 J. Phys. Chem. A, Vol. 109, No. 17, 2005
Horn et al.
with MgSO4. The product was purified by chromatography using
repeated every 0.4 MHz, which corresponds to the bandwidth
of the Fabry-Perot cavity, to cover the desired frequency region.
Molecular transitions observed during this initial search were
subsequently recorded using a higher resolution. The central
frequencies of the lines are determined by averaging the
frequencies of the two Doppler components after transformation
of 4096 data points of the time domain signal, leading to a
resolution of 2.4 kHz per point. The accuracy of frequency
measurements is estimated to be better than 3 kHz. The line
width for a typical well-resolved line is 10 kHz.
µa- and µb-type transitions were observed for the 70Ge, 72Ge,
and 74Ge isotopomers. These were readily assigned to the ac
conformer using the results from the assigned Stark spectrum
discussed below. The optimal MW power required to polarize
the molecules was found to be around 40 mW for µa-type
transitions and 4 mW for µb-type transitions, which indicates
that µb > µa as predicted by the quantum chemical calculations
below. All the observed b-type transitions were split into two
components. The splittings are a few tens of kilohertz (see Table
6).
IR Experiment. The IR spectra were recorded in the 500-
4000 cm-1 range using a 120HR Bruker Fourier transform
interferometer equipped with a KBr beam splitter, a Globar
source, and a liquid nitrogen-cooled mercury cadmium telluride
detector. A gas cell equipped with 3 mm ZnSe windows and a
multiple-pass optical system23 was used. The total optical path
length was adjusted to 10 m when recording the spectra. The
gas-phase spectrum of allylgermane is shown in Figure 2. The
corresponding spectra of the deuterated species CH2dCHs
CHDsGeH3, CH2dCHsCH2sGeD3, and CH2dCDsCH2s
GeH3 are shown in Supporting Information, Figures 1S-4S.
All spectra were taken at -40 °C. The resolution is 0.5 cm-1
in each case. The pressure of these species was 0.340 mbar for
the parent species, 0.405 mbar for CH2dCHsCHDsGeH3,
0.280 mbar for CH2dCHsCH2sGeD3, and 0.432 mbar for
CH2dCDsCH2sGeH3, respectively.
alumina. Yield: 92%. Isotopic purity: >97%. 1H NMR
2
(CDCl3): δ 2.48 (s, 2H, JSnH ) 70.9 Hz, CH2sSn), 4.81 (s,
4
4
1H, JSnH ) 21.9 Hz, CH(H)dC), 4.99 (s, 1H, JSnH ) 22.4
3
Hz, CH(H)dC), 7.39 (m, 9H, SnPh3); 7.56 (m, 6H, JSnH
)
49.8 Hz, SnPh3). 13C NMR (CDCl3): δ 17.4, 112.0, 128.3,
128.8, 135.3 (1JCD ) 23.3 Hz), 136.8, 138.1. HRMS (LSIMS
with cesium gun, positive mode, matrix: mNBA) m/z: [M -
H]+ calcd for C21H16D120Sn, 390.0415; found, 390.042.
2-Deutero-2-propenyltrichlorogermane was prepared starting
from 2-deutero-2-propenyltriphenylstannane and germanium
tetrachloride using the experimental procedure reported above.
1
Yield: 72%. Isotopic purity: 96%. H NMR (CDCl3): δ 2.89
(s, 2H, CH2sGe); 5.39 (s, 2H, CH2dC). 13C NMR (CDCl3):
δ 37.0, 121.4, 125.7 (1JCD ) 24.5 Hz).
2-Deutero-2-propenylgermane was prepared starting from
2-deutero-2-propenyltrichlorogermane and LiAlH4 using the
experimental procedure reported above. Yield: 88%. Isotopic
1
3
purity: 96%. H NMR (CDCl3): δ 1.93 (m, 2H, JHH ) 3.1
3
3
Hz, JHD ) 1.0 Hz, CH2sGe), 3.61 (t, 3H, JHH ) 3.1 Hz,
GeH3), 4.88 (s, 1H, CH(H)dC), 4.99 (s, 1H, CH(H)dC). 13C
NMR (CDCl3): δ 14.0, 113.1, 135.9 (1JCD ) 23.3 Hz).
Synthesis of 2-Propenylgermane-d3.18 2-Propenylgermane-
d3 was prepared starting from the 2-propenyltrichlorogermane
and LiAlD4 using the experimental procedure reported above.
Yield: 88%. Isotopic purity: >94%. 1H NMR (CDCl3): δ 1.94
(d, 2H, 3JHH ) 7.6 Hz, CH2sGe), 4.88 (dm, 1H, 3JHHcis ) 9.8
3
Hz, CH(H)dC), 4.99 (dm, 1H, JHHtrans ) 15.8 Hz, CH(H)d
C); 5.91 (ddt, 1H, 3JHHtrans ) 15.8 Hz, 3JHHcis ) 9.8 Hz, 3JHH
7.6 Hz, CHdC). 13C NMR (CDCl3): δ 13.8, 113.3, 136.2.
)
MW Stark Spectrometer Experiment. The MW spectrum
of the title compound was studied using the Oslo Stark
spectrometer, which is described briefly in ref 20. A 2 m brass
Stark cell was utilized. The 11.5-51 GHz spectral region was
investigated, with the cell cooled to dry ice temperature (-78
°C). The pressure was a few pascals when the spectra were
recorded using a program by Grønås.21 The accuracy of the
spectral measurements was better than (0.10 MHz, and the
maximum resolution was about 0.4 MHz.
The compound was kept for several months in a refrigerator
at about -30 °C or in a Dewar flask at dry ice temperature
when not in use. The compound was found to polymerize easily.
In fact, polymerization occurred even when the compound was
kept under these conditions. However, gaseous allylgermane
held at a pressure of about 10 Pa showed no signs of
decomposition or polymerization in the brass MW cell over the
course of 6-8 h. The spectra were taken at a pressure of a few
pascals. No impurities were noted in the MW spectrum.
Fourier Transform MW Spectrometer Experiments. Ro-
tational spectra were recorded for the parent species in the 6-20
GHz spectral range using the Lille Fourier transform MW
spectrometer.22 A gas mixture formed from 3 mbar of allylger-
mane with neon as the carrier gas to a total pressure of 1 bar
was prepared. Gas pulses were then expanded into the vacuum
chamber through a pulsed nozzle to create a supersonic jet. As
the nozzle is inserted in the center of the fixed mirror of the
Fabry-Perot cavity, the supersonic expansion is parallel to the
optical axis of the cavity. Each transition is divided into two
Doppler components.
Results
Computational Methods. The quantum chemical calculations
were made in Lille with the MolPro200024 and Gaussian 03
programs25 and in Oslo using the latter program.
It is known that ab initio electronic structure calculations
employing a large basis set and the second-order Møller-Plesset
(MP2) perturbation treatment for electron correlation26 yield
fairly accurate structures and consequently predict rotational
constants that are rather close to the experimentally determined
ones.27 This will of course facilitate the assignments of the MW
spectra.
With this in mind, calculations were performed at the MP2
level of theory to get the best possible starting point. The
structures of the ac and the sp conformers were fully optimized,
with no geometrical restrictions imposed. Three different basis
sets were used. The first one is Dunning’s correlation consistent
basis set with polarized valence electrons and diffuse functions
at the triple-ú level.28,29 The other two are the standard cc-pVTZ
for H and C. For Ge, two different small-core relativistic
pseudopotential correlation consistent basis sets called cc-pVTZ-
PP30 and SDB-cc-pVTZ31 were employed.
These three basis sets give almost identical results, except
for the GesH and GesC bond lengths. The SDB-cc-pVTZ
gives the largest values and the cc-pVTZ-PP the smallest ones.
For instance, for the Ge4sH10 bond length (Figure 1), the
results are for the ac form (in pm): 150.5 (cc-p-VTZ-PP); 151.9
(aug-cc-pVTZ); and 153.5 (SDB-cc-pVTZ). The equilibrium
Large spectral region surveys were conducted from 11.5 to
16.5 GHz, using the fast (low-resolution) scan mode facilities
of the spectrometer.22 In this operating mode, about 10 free
induction decays were averaged and Fourier transformed at a
repetition rate of 1.5 Hz. This operation is then automatically

Allylgermane Properties by MW and IR Spectroscopy
J. Phys. Chem. A, Vol. 109, No. 17, 2005 3825
Figure 2. Gas-phase IR spectrum of H2CdCHCH2GeH3 taken at a pressure of 0.340 mbar and a temperature of -40 °C.
TABLE 1: Ab Initio MP2/aug-cc-pVTZ Structuresa,b of the
Anticlinal and Synperiplanar Conformers of Allylgermane
GesH bond length has been accurately determined for three
germyl compounds: GeH4 (151.6),14 GeH3F (151.5),4 and GeH3-
Cl (151.6).3 These values are extremely close and indicate that
the GesH bond length in the ac conformer should be close to
151.6 pm too. To confirm this statement, we performed ab initio
calculations for GeH4 using the same basis sets. The results are
(in pm): 149.9 (cc-p-VTZ-PP); 151.2 (aug-cc-pVTZ); and 153.0
(SDB-cc-pVTZ). This indicates that the equilibrium value of
GesH should be close to 152.0 pm.
To estimate the error of the GesC bond length, it is possible
to use methylgermane where rs(GesC) ) 194.5(5) pm.8 The
same calculations were repeated for this molecule. They give
for the GesC bond length (in pm): 196.2 (SDB-cc-pVTZ) and
193.7 (aug-cc-pVTZ). The cc-pVTZ-PP basis set does not
converge because of the excessive mixing of frozen core and
valence orbitals. Thus, the equilibrium GesC bond length
should be close to 196.0 pm in the ac conformer.
These results indicate that the aug-cc-pVTZ basis set gives
the best results, probably by an accidental compensation of
errors. This is confirmed by comparing the experimental (Table
3) and ab initio rotational constants where the smallest errors
are found with the aug-cc-pVTZ basis set. For this reason, only
the structure obtained at the MP2/aug-cc-pVTZ level of theory
is given in Table 1. The rotational constants for the 74Ge
isotopomer calculated from the refined structures, dipole mo-
ment components of the same isotopomer, and energy differ-
ences are found in Table 2.
A few comments about the structures of the two rotamers
are warranted. The sp conformer has a symmetry plane (Cs
symmetry). The important C1C2C3Ge4 dihedral angle in ac is
predicted to be 106.2°, about 14° from the idealized value
(120°). The ac rotamer is preferred relative to sp by 5.6 kJ/
mol. It is possible that this energy difference reflects repulsive
forces in the sp conformer, increasing its energy. The evidence
for existence of repulsive forces is seen in the C2C3Ge4 angle,
which is calculated to increase from 110.3° in ac to 116.0 in
sp (Table 1).
ac conformer
sp conformer
Bond Lengths
133.7
C1dC2
133.6
108.1
108.2
149.8
108.6
194.5
109.3
109.3
151.7
151.8
151.8
C1sH5
C1sH6
C2sC3
C2sH7
C3sGe4
C3sH8
C3sH9
Ge4sH10
Ge4sH11
Ge4sH12
108.1
108.3
149.0
108.6
195.1
109.1
109.0
151.9
151.7
151.8
Angles
121.2
121.0
124.9
118.6
110.3
111.1
110.9
110.6
109.0
109.1
C2C1H5
C2C1H6
C1C2C3
C1C2H7
C2C3Ge4
C2C3H8
C2C3H9
C3Ge4H10
C3Ge4H11
C3Ge4H12
120.9
121.9
126.0
117.9
116.0
109.6
109.6
108.7
110.5
110.5
Dihedral Angles
178.0
H5C1C2C3
H5C1C2H7
H6C1C2C3
C1C2C3Ge4
C1C2C3H8
C1C2C3H9
C2C3Ge4H10
C2C3Ge4H11
C2C3Ge4H12
180.0
0.0
0.0
0.2
-2.0
-106.2
134.2
0.0
-122.4
122.4
180.0
60.4
14.1
-117.4
65.0
-54.2
-60.4
a Bond lengths in picometers; angles in degrees. b Atom numbering
is given in Figure 1.
distortion constants of the Watson A reduction33 were calculated
for the 74Ge isotopomer and are listed in Table 2.
The harmonic (or quartic) centrifugal distortion constants and
vibrational frequencies are other parameters of interest in this
investigation. The harmonic force field needs to be known to
calculate these parameters. This force field was calculated with
Becke’s density functional theory procedure, B3LYP,32 using
the 6-311G(3df,2pd) basis set. The five quartic centrifugal
It should be stated that all the B3LYP vibrational frequencies
were positive for both rotameric forms. This indicates that both
ac and sp represent minima (i.e., are “stable”) on the potential
energy hypersurface.34 The energy difference between these two
rotamers was calculated to be 9.2 kJ/mol by this method, nearly
twice as much at the MP2 value given above.

3826 J. Phys. Chem. A, Vol. 109, No. 17, 2005
Horn et al.
TABLE 2: Rotational Constants (MHz),a Centrifugal
Distortion Constants (kHz),b Dipole Moments (10-30 C m),c
and Relative Energiesd of the Anticlinal and Synperiplanar
Conformers of Allylgermane
and fairly dense spectrum. This was expected because the
quantum chemical calculations above predict rather small dipole
moments for both sp and ac. There are also several low-
frequency vibrational fundamentals that will have a significant
population even at -78 °C. Five of these vibrations are below
500 cm-1 in both rotamers according to the B3LYP calculations.
Moreover, germanium has several isotopes. The most abundant
ones are 70Ge (20.5%), 72Ge (27.4%), and 74Ge (36.5%). The
remaining two isotopes, 73Ge and 76Ge, are each present in
concentrations of less than 8% of the total. This distribution of
isotope concentration will lead to a further reduction of the
intensities of the MW lines.
ac
sp
Rotational Constants
14 616.7
A
B
C
11 130.5
2498.9
2119.4
2005.0
1928.3
Centrifugal Distortion Constantse
∆
∆
∆
1.25
-32.4
335
0.162
0.332
1.09
-5.22
24.4
0.216
-0.755
J
JK
K
δJ
The theoretical calculations above predict that the ac con-
former is preferred. This rotamer is seen in Table 2 to have the
major component of its dipole moment along the b-inertial axis
(1.69 × 10-30 C m). Searches were, therefore, first made for
δK
Dipole Moments
µa
0.12
1.69
0.07
1.70
1.22
2.24
0.0f
µb
µc
b
the Q-branch J1,J-1 r J0,J series of the most abundant (74Ge)
isotopomer, and these transitions were identified and assigned.
The frequencies of two further Q-branch series (K-1 ) 2 r 1
and K-1 ) 3 r 2) could now be predicted accurately. Q-branch
transitions with J values up to J ) 57 were soon assigned.
µtot
2.55
relative energy
0.0
5.6g
74Ge isotopomer. MP2/aug-cc-pVTZ calculations. b B3LYP/6-
a
311G(3df,2pd) calculations. c 1 D ) 3.335 64 × 10-30 C m. d In kJ/
mol. Total MP2 energy of ac: -5 761 428.03 kJ/mol. e A reduction.33
f For symmetry reasons. g The energy difference calculated by the G2
method was 6.6 kJ/mol, and the one calculated by the B3LYP method
was 9.2 kJ/mol.
b
Spectral lines attributable to the R-branch transitions were
then found after several alternative lines had been tested.
R-branch transitions with values of J up to J ) 35 were now
assigned. The hypothetical frequencies of a- or c-type lines could
now be calculated very accurately, but they were not found in
the Stark spectrum, presumably because they are too weak. This
is consistent with the very small dipole moment predicted for
these lines (Table 2). It should also be noted that no splittings
resulting from internal rotation of the germyl group were seen
in the Stark spectrum. Such splittings would have been
discovered if they had been larger than about 0.40 MHz.
TABLE 3: Relative Energies (kJ/mol) of the Anticlinal and
Synperiplanar Conformer of H2CdCHCH2XH3 with X ) C,
Si, Gea
G3B3 method
G2 method
(CCCX)a
∆Eb
∆Eb
allyl-CH3
allyl-SiH3
allyl-GeH3
ac
sp
ac
sp
ac
sp
119.6
0.0
107.6
0.0
105.0
0.0
0.0
0.7
0.0
5.4
d
0.0
1.2c
0.0
6.7
0.0
6.6
The spectroscopic constants obtained by Stark spectroscopy
were next used to predict further transitions that were subse-
quently measured using the Fourier transform spectrometer. Both
b-type as well as the much weaker a-type lines were now
assigned. All b-type lines were split into two components owing
to tunneling of the germyl group through its threefold barrier
(see Barrier to Internal Rotation section). There was no evidence
of splitting for the a-type transitions. The full spectrum which
also incorporates the transitions measured by Fourier transform
spectroscopy is shown in Table 1S in Supporting Information.
The average frequencies of the split b-type lines were used in
the fitting procedure.
The spectroscopic constants (A-reduction Ir representation33)
including the five quartic centrifugal distortion constants and
one sextic constant (φJ) are listed in Table 4. Inclusion of this
sextic constant was necessary to obtain a fit with an average
deviation comparable to the experimental uncertainty. The
transitions were weighted according to the inverse square of
their uncertainties in the fitting procedure. Sørensen’s program
ROTFIT38 was utilized. The weighted root-mean-square devia-
tion is minimized in this program.
d
a Dihedral angle calculated at the B3LYP/6-31G(d) level of theory.
b Energy relative to ac (0.0 kJ/mol). c Experimental value: 0.63(63)
kJ/mol. d Ge is not implemented in our version of the program.
The G235 procedure is known to give comparatively reliable
energy differences, and calculations at this level of theory were,
therefore, carried out next for the ac and sp rotamers. Although
germanium is a rather large atom, the errors of the energies are
largely systematic and would be expected to cancel to a large
degree in relative energy calculations. The energy difference
found in our G2 calculations was 6.6 kJ/mol with ac as the
preferred form, close to the MP2 value (5.6 kJ/mol) but lower
than the B3LYP result (9.2 kJ/mol).
This calculation was also repeated for allylsilane and 1-butene.
To check the accuracy of the energies, a variant of the
Gaussian-3 (G3) theory36 was also used for the latter two
molecules (the G3 theory is implemented only for atoms up to
Z ) 18 in our version of Gaussian 03). In the variant used,
G3B3,37 the geometries and zero-point energies are obtained
from B3LYP density functional theory [B3LYP/6-31G(d)]
instead of geometries from second-order perturbation theory
[MP2/6-31G(d), all electrons being correlated], and zero-point
energies are from Hartree-Fock theory. The G3B3 method is
slightly more accurate than the original G3 method. Its average
absolute deviation from experiment (for a total of roughly 300
molecules) is 4.1 kJ/mol, whereas it is 6.2 kJ/mol for the G2
theory. The results are gathered in Table 3.
The shifts in the rotational constants that accompany substitu-
tion of 74Ge by 72Ge or 70Ge can be predicted well. This made
it easy to assign the spectra of the corresponding isotopomers.
The spectra of these species are displayed in Tables 3S and 5S
in Supporting Information. The spectroscopic constants resulting
from least-squares fits are listed in Table 4. Interestingly, the
quartic centrifugal distortion constants in Table 4 for the most
abundant species are in quite good agreement with those listed
in Table 2 in all cases but δK, which differs from the
experimental one by more than 90%.
MW Spectra and Assignment of the ac Conformer. Survey
spectra taken using the Stark spectrometer revealed a rather weak

Allylgermane Properties by MW and IR Spectroscopy
J. Phys. Chem. A, Vol. 109, No. 17, 2005 3827
TABLE 4: Rotational (MHz), Quartic Centrifugal Distortion
(kHz), and Sextic Centrifugal Distortion Constants (Hz)a of
the Ground Vibrational State of the ac Conformer of
Allylgermane
TABLE 6: Transitions and Parameters Used To Determine
the Barrier to Internal Rotation of the Germyl Group of the
74Ge Isotopomera,b
νA - νE obs. - calc.
74Ge isotopomer
72Ge isotopomer
70Ge isotopomer
J′ K-1
′
K+1
′
r
J′′ K-1′′ K+1′′ (MHz)
(MHz)
A
B
14 751.0877(31)
1967.793 34(58)
1895.385 76(59)
1.586 74(59)
-40.8215(87)
394.21(23)
0.229 23(10)
1.780(31)
14 759.9809(37)
1982.146 46(65)
1908.848 60(65)
1.6197(16)
-41.138(13)
402.3(14)
0.233 84(10)
1.765(35)
0.002 748(36)
131
147 69.3268(53)
1997.2145(32)
1922.9795(31)
1.6515(93)
-41.305(23)
384.1(31)
0.238 67(12)
1.648(42)
0.002 813(36)
115
4
5
6
7
1
1
2
3
1
1
1
1
1
1
1
1
3
4
5
6
1
0
1
2
4
5
6
7
0
1
2
3
0
0
0
0
0
0
0
0
4
5
6
7
0
1
2
3
0.043
0.043
0.044
0.046
0.048
0.042
0.048
0.044
0.002
0.002
0.002
0.000
-0.004
0.002
C
∆
∆
∆
J
JK
K
δJ
-0.004
0.000
δK
φJb
Nc
0.002 631(35)
167
2.78
a See text. b Parameters kept fixed: IR ) 0.630 u nm2, λa ) 0.6406,
λb ) -0.496 35, λc ) 0.083 86, â ) 0.074 472 rad, γ ) 0.161 76 rad.
From fit V3 ) 6561(17) J/mol, root-mean-square dev. ) 0.0025 MHz.
See Woods for the definitions of the parameters.40 These parameters
have been calculated using the structure given in Table 1.
rmsd
2.85
2.55
a A-reduction Ir representation.33 b Further sextic constants preset
at zero. c Number of lines used in the fit. d Root-mean-square deviation
from a weighted fit.
from the experimental rotational constants. This is evidence that
the said dihedral angle is indeed close to 106°.
TABLE 5: Rotational (MHz), Quartic Centrifugal Distortion
(kHz), and Sextic Centrifugal Distortion Constants (Hz)a of
the First Excited State of the Torsion around the C2sC3
Bond of the ac Conformer of Allylgermane
It was mentioned above that bond lengths involving germa-
nium obtained in these calculations were close to the expected
values. Very small changes in bond lengths, angles, and dihedral
angles would produce the observed differences between the
observed and the calculated rotational constants. It is, therefore,
concluded that the structure presented for the ac rotamer in Table
1 is a good approximation of the equilibrium structure.
Searches for the sp Conformer. Extensive searches were
carried out for the sp rotamer using both Stark and Fourier
transform spectroscopy, though no assignment could be made.
The same was found using IR spectroscopy (see below). It is
concluded that this conformer must be a high-energy form of
the molecule in agreement with the theoretical predictions above
(5.6-9.2 kJ/mol), if it exists at all as a stable rotameric form
of the molecule.
74Ge isotopomer
72Ge isotopomer
70Ge isotopomer
A
B
14 747.096(20)
1978.0491(33)
1900.8567(33)
1.6440(85)
-40.199(24)
398.5(48)
0.246 31(11)
3.477(30)
0.002 823(39)
104
14 755.767(22)
1992.4737(38)
1914.3251(38)
1.621(13)
-40.517(29)
405.7(57)
0.251 13(11)
3.539(38)
0.002 939(34)
87
14 764.878(25)
2007.6217(69)
1928.4653(69)
1.645(24)
-40.788(32)
402.0(61)
0.256 42(12)
3.604(43)
0.003 128(39)
76
C
∆
∆
∆
J
JK
K
δJ
δK
φJb
Nc
rmsd
1.99
1.97
1.97
a -dFootnotes are the same as for Table 4.
Barrier to Internal Rotation of the Germyl Group. Most
lines measured by Fourier transform MW were found to be split
into doublets as a consequence of the internal rotation of the
germyl group, as already mentioned. The observed splittings
(Table 6) are nearly identical for all Ge isotopic species. Only
those corresponding to the main isotopic species (74Ge) were,
therefore, analyzed. As the number and diversity of the splittings
are small, only the potential barrier could be fitted. Conse-
quently, all the structural parameters, that is, the moment of
inertia of the germyl group around the symmetry axis (IR) and
the direction cosines of the symmetry axis of the top (λa, λb,
and λc), were calculated from the MP2/aug-cc-pVTZ structure
given in Table 1. Woods’ program40 was used for the fit.
The value of the barrier to internal rotation of the germyl
group found in this manner (V3 ) 6.561(17) kJ/mol) should be
compared to those of H3GeCH3 (5.19),8 H3GeCH2F (5.81(17)),12
H3GeCH2Cl (7.28(17)),13 H3GeCH2CH3 (5.98(12)),9 and cy-
clopropylgermane (5.58(20) kJ/mol).10 It is, therefore, concluded
that the barrier to internal rotation of the germyl group of the
title compound is rather typical for compounds where the said
group is attached to a sp3-hybridized carbon atom.
It is interesting to compare the barrier to internal rotation of
the XH3 top of the three allyl-XH3 molecules (X ) C; Si and
Ge). The barrier to internal rotation of the methyl group of the
ac form of H2CdCHCH2CH3 is 13.22 kJ/mol.41 A barrier of
8.74 kJ/mol was found for the silyl top in the corresponding
rotameric form of H2CdCHCH2SiH3.42 The fact that the barrier
of the germyl group is 6.561(17) kJ/mol in allylgermane is
consistent with increased distance between X and the atom to
which the XH3 group is attached, reducing the interaction
between the top and the frame.
The ground-state transitions in the Stark spectrum were
accompanied by less intense lines presumably belonging to
vibrationally excited states. One such state, assumed to be the
first excited state of the lowest fundamental, was assigned. The
spectra of the 74Ge, 72Ge, and 70Ge isotopomers of this excited
state are listed in Supporting Information, Tables 2S, 4S, and
6S. The spectroscopic constants are displayed in Table 5.
Relative intensity measurements performed as described in
ref 39 yielded 92(20) cm-1 for this vibrational mode. The lowest
fundamental vibration found in the B3LYP calculations has a
frequency of 88 cm-1. This mode is the torsion around the C2s
C3 bond (Figure 1).
It was not possible to determine the dipole moment from the
Stark effect in this case because the low-J lines normally used
for this purpose were too weak to allow quantitative measure-
ments to be made.
Structure of the ac Conformer. Comparison of the experi-
mental (Table 4) and the MP2/aug-cc-pVTZ (Table 2) rotational
constants of the 74Ge isotopomer calculated from the structure
of Table 1 reveals the differences between the experimental and
theoretical values to be 0.9, -1.9, and -1.7% in the cases of
A, B, and C, respectively. A positive difference of roughly 1%
in each case would have been expected if an accurate equilib-
rium structure had been available.
Interestingly, the size of the second moment defined as Pcc
) (Ia + Ib - Ic)/2, where Ia, Ib, and Ic are the principal moments
of inertia, is sensitive to the value of the C1C2C3Ge4 dihedral
angle. The value calculated for Pcc from the structure in Table
1 is 12.28 × 10-20 u m2, close to 12.22 × 10-20 u m2 calculated

3828 J. Phys. Chem. A, Vol. 109, No. 17, 2005
Horn et al.
intensityb
TABLE 7: IR Spectrum and Assignments of
IR Spectrum and Assignments. The gas-phase IR spectrum
of allylgermane in the 500-4000 cm-1 region is given in Figure
2. It is evident from this figure that parts of the spectrum are
quite complicated, sometimes making the assignments of the
various bands difficult. Use has been made of the spectra of
the three deuterated species CH2dCHsCHDsGeH3, CH2d
CHsCH2sGeD3, and CH2dCDsCH2sGeH3 in the assignment
procedure. These spectra are given in Supporting Information,
Figures 1S-4S. The B3LYP predictions made for the vibrational
fundamentals were also helpful, as were the IR spectra of several
related compounds.43-45
It is seen that the spectral region between 1050 and 500 cm-1
is rather complicated with several overlapping absorption bands.
By making use of the expected isotope effects of the sCHDs
methylene group in CH2dCHsCHDsGeH3 (Figure 1S, Sup-
porting Information) and of the GeD3 group in CH2dCHs
CH2sGeD3 (Figure 2S), the assignment of the fundamental
vibrational bands is considerably simplified. The tri-deuteration
of the germane group induces a significant shift of its deforma-
tion vibrations. The average ratio of νobs(sGeH3)/νobs(sGeD3)
is found to be 1.39.
The vibrational modes of the methylenesCH2 group appear-
ing in this same region, namely, the scissoring, wagging,
twisting, and rocking, are shifted in the spectrum of CH2dCHs
CHDsGeH3 and have been unambiguously identified. Conse-
quently, all other vibrational bands in this region that are not
sensitive to the isotopic effect are attributed to the vibrations
of the vinyl group.
The 1050-2700 cm-1 spectral range is much less complicated
than the previous region (Figure 2), allowing assignments to
be made readily.
However, the region around 3000 cm-1 is quite complex. The
isotopic shift of the CsH stretching vibration of the vinyl group
produced by CH2dCD-CH2sGeH3 (Figure 3S) was useful for
making definite assignments here. The spectrum of the parent
species (CH2dCHsCH2sGeH3) with assignments and intensi-
ties is listed in Table 7. Similar information for the three
deuterated species is listed in Table 7S in Supporting Informa-
tion. The IR spectra of the parent and deuterated species are
compared in Figure 4S.
The theoretical calculations above predict the existence of
two stable rotameric forms of allylgermane, the sp and the ac
conformers, with ac as the favored one. The B3LYP harmonic
frequencies are nearly the same for these two forms. The close
proximity of the fundamental vibrations of sp and ac makes it
difficult to find sp provided it is present in a concentration below
about 10% of the total. The IR spectrum, therefore, corroborates
the MW findings and the quantum chemical calculations in that
ac is considerably more stable than the hypothetical sp
conformer.
H2CdCHCH2GeH3
assignmenta
frequency
ν1
dCH2 antisymmetric stretching
dCH2 symmetric stretching
(dCHs bend out-of-plane)
dCHs stretching
sCH2s symmetric stretching
sCH2s antisymmetric stretching
GeH3 stretching
GeH3 stretching
GeH3 stretching
(dCHs out-of-plane bending)
(dCH2 wagging)
(GeH3 deformation)
CdC stretching
sCH2s deformation
dCH2 deformation
dCHs in-plane bending
sCH2s wagging
sCH2s twisting
CsC stretching
dCHs out-of-plane bending
dCH2 rocking
dCH2 wagging
GeH3 deformation
GeH3 deformation
3092
3052
2985
3010
2952
2922
2111
2082
2078
1973
1810
1767
1639
1431
1405
1299
1199
1159
1040
989
920
903
883
829
754
720
664
636
s
ν2
m
w
m
w
m
vs
vs
vs
m
m
w
s
m
w
w
m
m
m
s
w
vs
s
vs
s
m
w
vw
3ν15
ν3
ν4
ν5
ν6
ν7
ν8
2ν15
2ν17
2ν18
ν9
ν10
ν11
ν12
ν13
ν14
ν15
ν16
ν17
ν18
ν19
ν20
ν21
ν22
ν23
ν24
GeH3 deformation
sCH2s rocking
dCH2 twisting
GesC stretching
a See text. b vs (very strong), s (strong), m (medium), w (weak), and
vw (very weak). dCH2, vinyl group; sCH2s, methylene group.
(3)° in the ac conformer of 1-butene,41 rather different from
106.8(11)° in allylsilane,47 which is nearly the same as 106.4°
found for allylgermane (Table 1). The conformational properties
of allylgermane are, thus, much more similar to that of
allylsilane than to that of 1-butene. The reason this dihedral
angle in allylsilane and allylgermane is so different from that
in 1-butene is not obvious. It is possible that the d orbitals on
Si and Ge play a role here.
There has been speculation as to whether the sp form of
allylsilane is indeed a stable conformer of this compound
(minimum on the potential energy hyper/surface) or whether it
represents a maximum and is consequently a transition state.42
σ-π hyperconjugation might cause such a behavior according
to this study.42 A similar situation cannot be completely ruled
out for allylgermane, although the quantum chemical calcula-
tions above indicate that the sp form is indeed a stable rotameric
form because positive normal vibrations were always predicted
in the theoretical calculations.
Acknowledgment. We thank Cand. Scient. Terje Grønås for
his continuous efforts to optimize the LabView programs. Dr.
George C. Cole is thanked for his thorough reading of this
manuscript and for his help in improving the language. A grant
from the French-Norwegian Aurora Program to J.-C.G. and
H.M. is gratefully acknowledged. J.-C.G. thanks the Centre
National d’Etudes Spatiales (CNES) for financial support. H.M.
thanks the Research Council of Norway (Programme for
Supercomputing) for a grant of computer time.
Discussion
It is interesting to compare the structural and conformational
properties of the two related molecules 1-butene (H2CdCHCH2-
CH3) and allylsilane (H2CdCHCH2SiH3) to the present study
of allylgermane (H2CdCHCH2GeH3).
1-Butene exists as a mixture of the sp and ac conformers.41,44
The ac form is 0.63(63) kJ/mol more stable than sp41,44 in this
case. A different situation exists for allylsilane. This compound
has been studied by electron diffraction,46 MW spectroscopy,47
IR spectroscopy,42 and quantum chemical calculations.42 Only
the ac rotamer has been found in the experimental investigations.
The CdCsCsX (X ) C, Si, Ge) dihedral angle determines
the conformation of these three compounds. This angle is 119.9-
Supporting Information Available: Tables 1S-6S contain
the MW spectra, the IR spectra are shown in Figures 1S-4S,
and Table 7S shows the comparison of observed vibrational
frequencies for allylgermane and its deuterated derivatives. This
material is available free of charge via the Internet at http://
pubs.acs.org.

Allylgermane Properties by MW and IR Spectroscopy
J. Phys. Chem. A, Vol. 109, No. 17, 2005 3829
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