Reprint of: Nitrile functionalized organogermane chalcogenide clusters with hetero-(nor-)adamantane cores

Article abstract of DOI:10.1016/j.jorganchem.2016.09.011

By the synthesis of Cl₃Ge(CH₂)₂CN (1) and subsequent reaction with sodium monochalcogenides, adamantane-type [(NC(CH₂)₂Ge)₄Ch₆] (Ch = S (2), Se) and noradamantane-type [(NC(CH

Full text of DOI:10.1016/j.jorganchem.2016.09.011

Journal of Organometallic Chemistry xxx (2016) 1e5
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Reprint of: Nitrile functionalized organogermane chalcogenide
clusters with hetero-(nor-)adamantane cores*
Samuel Heimann, Günther Thiele, Stefanie Dehnen*
€
Fachbereich Chemie, Philipps-Universitat Marburg, Hans-Meerwein-Strasse, D-35043 Marburg, Germany
a r t i c l e i n f o
a b s t r a c t
Article history:
By the synthesis of Cl3Ge(CH2)2CN (1) and subsequent reaction with sodium monochalcogenides,
adamantane-type [(NC(CH2)2Ge)4Ch6] (Ch ¼ S (2), Se) and noradamantane-type [(NC(CH2)2Ge)4Te5] (3)
were obtained. The compounds represent the first nitrile-functionalized tetrel chalcogenide clusters and
the first nitrile-functionalized clusters of the named architectures, and are thus potential precursor for
novel reaction pathways to multifunctional core-shell compounds.
Received 19 January 2016
Received in revised form
5 March 2016
Accepted 22 March 2016
Available online xxx
© 2016 Elsevier B.V. All rights reserved.
Dedicated to Professor Heinrich Lang on the
occasion of his 60th birthday.
Keywords:
Organo-germanium chemistry
Hybrid clusters
Germanium chalcogenide clusters
Nitrile ligands
X-ray diffraction
DFT calculations
1. Introduction
restrict the variety of potentially interesting organic substituents
that can be directly attached to the Ge atoms. Hence, starting with
Organotetrel chalcogenide clusters, that is, binary clusters of
groups 14 and 16, have shown intriguing physical and chemical
properties, in particular if the respective ligands comprise func-
tional organic groups [1]. Such compounds can therefore be
regarded as core-shell hybrids: via an appropriate choice of the
elemental combination, the inorganic core can be designed for e.g.
opto-electronic properties, while the organic periphery can be
adjusted for further chemical derivatization or complexation to-
wards transition metal compounds [2e4].
Certain restrictions exist for the integration of functional groups
in the ligand shell of compounds of the general type [(RfTt)xChy],
with Rf ¼ functionalized organic ligand, Tt ¼ Si, Ge, Sn, and Ch ¼ S,
Se, Te. Strong coordination of a donor group at the ligand towards
the core unit, or redox reactions with the chalcogenide source
Cl3GeeRf in a standard reaction with H2Ch or TMS2Ch, only keto
and carboxylate groups [5], or silyl substituents [6] could so far be
integrated in the ligand shell of RfGe/E clusters that are known in
one of three predominant core architectures: the adamantane type,
the double-decker-type, both of the general formulae [(RTt)4Ch6]
[7,8], or the noradamantane-type structure [(RTt)4Ch5] [9]. Even
though the functional groups allow for further derivatization, e.g.
via reaction with hydrazine, organic hydrazines, hydrazones or
hydrazides [10], the follow-up chemistry is fairly restricted. Hence,
novel functionalities are desirable in regard of new potential
derivatization approaches of the organic ligand decoration. Here,
we would like to present our results on the synthesis of Ge/E cluster
compounds that are terminated by nitrile groups, and discuss their
potential for further derivatization, e.g. with respect to click
chemistry or hydrogenation, or upon utilization of the coordinating
properties of the nitrogen lone pair for further (transition) metal
ion coordination.
DOI of original article: http://dx.doi.org/10.1016/j.jorganchem.2016.03.026.
This article is a reprint of a previously published article. For citation purposes,
*
please use the original publication details; [Journal of Organometallic Chemistry],
[813/C], pp. [36e40].
* Corresponding author.
E-mail address: dehnen@chemie.uni-marburg.de (S. Dehnen).
http://dx.doi.org/10.1016/j.jorganchem.2016.09.011
0022-328X/© 2016 Elsevier B.V. All rights reserved.
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j.jorganchem.2016.09.011

2
S. Heimann et al. / Journal of Organometallic Chemistry xxx (2016) 1e5
2. Materials and methods
(1577), S ¼ 0.723. 1H NMR (300 MHz, CDCl3)
d: 1.78e1.85 (m, 2H,
CH2), 2.45e2.54 (m, 2H, CH2) ppm. 13C (75 MHz, CDCl3)
(GeeCH2), 14.4 (CeCH2) 118.8 (CeN) ppm.
d: 36.5
2.1. General
All manipulations were performed under strict exclusion of
oxygen and moisture, applying standard Schlenk and glovebox
techniques. 1,1,3,3-Tetramethyldisiloxane (purchased from Sigma-
Aldrich in 97% purity), GeCl4 (purchased from Sigma-Aldrich in
99.99% purity) and Na2S$9H2O (purchased from Acros Organics in
98þ% purity) were used as received. Na2Se and Na2Te were syn-
thesized from equimolar amounts of the elements in liquid
ammonia according to known literature procedures [11]. Et2O and
THF were freshly distilled from sodium and benzophenone, MeOH
was dried with Mg and subsequent distillation, H2O has been
degassed and saturated with Ar prior use. ESI spectra were recor-
ded on a Finnigan MAT 95S. CHN analyses were performed on a
Vario MicroCube, EDX on a Noran Instruments Vovayer 4.0 with a
CamScan CS 4DV electron microscope with an acceleration voltage
of 20 kV and an accumulation time of 100 s. NMR spectra were
obtained from a Bruker DRX 300 (1H, 13C) or DRX 400 (125Te) in
CDCl3. X-ray diffraction was performed at T ¼ 100 K on a Stoe IPDS2,
equipped with graphite monochromator. All structures were solved
by direct methods in WinGX and Olex2 [12], and refined by full-
matrix least-squares refinement against F2 in SHELXL-2015 [13].
Absorption correction were performed numerically including
shape optimization with Stoe X-Area. CCDC 1448281-1448283
contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif.
2.4. Synthesis of [(NC(CH2)2Ge)4Se6]
A solution of 0.50 g (2.15 mmol) of 1 in 50 mL of THF is added to
a suspension of 0.30 g (2.40 mmol, 1.1 eq) Na2Se in 100 mL of THF
under constant stirring. The reaction mixture is stirred for 30 h
under exclusion of light. After filtration, the resulting solution is
evaporated to a final volume of 75 mL and left for 15 h. 3 forms as
colorless blocks. MS (ESIþ) m/z ¼ 981.33 (Mþ). CHN (meas./calc.)/%:
C (14.67/14.70), H (1.65/1.64), N (5.68/5.71). EDX ratio (meas./calc.)
Ge/Se (1:1.56/1:1.5). The crystal quality has so far not been good
enough for the collection of a satisfying and publishable data set;
however, the cluster composition and structure was unambigu-
ously identified. According to 1H and 13C NMR data, the CH2CH2CN
ligands are retained on the cluster molecules in solution. 77Se NMR
data could not be detected within the experimental noise.
2.5. Synthesis of 3
Same procedure as for [(NC(CH2)2Ge)4Se6], applying 0.50 g
(2.15 mmol) of 1 and 0.42 g (2.42 mmol,1.1 eq) Na2Te with the same
amount of solvents. After reduction of the solvent volume, 3 crys-
tallizes after 4 h as orange blocks in approx. 34% yield (0.21 g,
0.18 mmol) with respect to 1. MS (ESIþ) m/z ¼ 1145.35 (Mþ). CHN
(meas./calc.)/% C (12.52/12.58), H (1.40/1.41), N (4.88/4.89). EDX
ratio (meas./calc.) Ge/Te (1:1.18/1:1.25). Crystallographic data for
C
a
a
12H16Ge4N4Te5 (Mw ¼ 1144.65 g/mol): triclinic space group P1,
¼
10.8179(6) Å,
b
¼
11.0425(6) Å,
c
¼
12.0025(6) Å,
¼ 102.642(4)ꢀ,
b
¼ 113.904(4)ꢀ,
g
¼ 94.980(4). R1 (refl.) ¼ 0.0524
2.2. Synthesis of 1
(3729), wR2 (refl.) ¼ 0.1374 (5244), S ¼ 0.953. 1H NMR (300 MHz,
CDCl3) d C
: 2.60e3.11 (m, 2H, CH2), 1.92e2.25 (m, 2H, CH2) ppm. 13
15.0 mL (84.9 mmol, 1.0 eq) of 1,1,3,3-tetramethydisiloxane are
slowly added to a solution of 10.0 mL (87.6 mmol, 1.0 eq) GeCl4 in
30 mL of Et2O. The reaction mixture is heated to reflux for 1.5 h and
allowed to cool to room temperature. The resulting reaction
mixture is added to a solution of 6.3 mL (96.2 mmol, 1.1 eq) of
acrylonitrile in 10 mL of Et2O and stirred for 20 h. 1 can be obtained
after vacuum distillation (80 ꢀC, 10ꢁ3 mbar) as colorless liquid in
quantitative yield (19.8 g, 84.9 mmol). After cooling, 1 forms a light-
yellow solid. CHN (meas./calc.)/%: C (16.94/15.46), H (2.08/1.73), N
(5.83/6.01). Crystallographic data for C3H4Cl3GeN (Mw ¼ 233.01 g/
mol): monoclinic space group P21/m, a ¼ 6.1541(7) Å, b ¼ 6.8845(4)
(75 MHz, CDCl3)
d: 35.7e38.5 (GeeCH2), 15.7e22.7 (CeCH2),
119.7e121.7 (CeN) ppm. 125Te NMR
(Te2 e Te4).
d: 21.71 ppm (Te1), e96.05 ppm
Density functional theory (DFT) calculations were done with the
program system TURBOMOLE [14a] employing the BeckeePerdew
86 (BP86) functional [14b,c] with def2-TZVP bases [14d] and
respective fitting bases [14e] for the evaluation of the Coulomb
matrix. Effective core potentials (ECPs) were used for Te atoms
(ECP-28) [14f]. Contour plots were generated with gOpenMol.[14g]
Å, c ¼ 9.4294(10) Å,
b
¼ 105.578(8)ꢀ. R1 (refl.) ¼ 0.0196 (980), wR2
3. Results and discussion
(refl.) ¼ 0.0427 (1119), S ¼ 0.944. 1H NMR (300 MHz, CDCl3)
d:
2.73e2.82 (m, 2H, CH2), 2.28e2.38 (m, 2H, CH2) ppm. 13C (75 MHz,
Starting out from our synthetic protocol that proved successful
for the generation of keto-functionalized chlorogermanes [15,16],
we reacted GeCl4 with acrylonitrile to yield Cl3Ge(CH2)2CN (1) in
almost quantitative yield after work-up procedure. Further re-
actions with chalcogenide sources Na2S$9H20, Na2Se, or Na2Te,
respectively, in appropriate solvents (see Materials and Methods
section) yielded adamantane-type [(NC(CH2)2Ge)4Ch6] (Ch ¼ S (2),
Se [17]) and noradamantane-type [(NC(CH2)2Ge)4Te5] (3), as illus-
trated in Scheme 1.
Compound 1 crystallizes in the monoclinic space group P21/m
with two formulae units in the unit cell. Its molecular structure is
depicted in Fig. 1. The GeeCl and GeeC bond lengths in 1 (GeeCl
2.1232(7), 2.1265(4) Å; GeeC 1.928(2) Å) are slightly or even
noticeably shorter than average values for reported single-bond
distances (GeeCl 2.150 Å, GeeC 2.004 Å) [18], whereas the C^N
bond length (1.141(3) Å) is in good agreement with those reported
(CalkeC^N 1.137 Å, CareC^N 1.138 Å; see also below) [18].
CDCl3) d: 25.8 (GeeCH2), 11.1 (CeCH2), 116.3 (CeN) ppm.
2.3. Synthesis of 2
A solution of 0.50 g (2.15 mmol) of 1 in 25 mL acetone is added to
a solution of 1.09 g (4.54 mmol, 2.1 eq) of Na2S$9H2O in a mixture of
25 mL H2O and 25 mL of acetone and vigorously stirred for 5 h
under exclusion of light. The volume of the reaction mixture was
reduced to 25 mL, the resulting precipitate washed with 0.5 mL H2O
and solved in MeOH. The resulting solution was layered with Et2O
to yield 2 after 5 d as colorless crystals in 80% yield (0.30 g,
0.43 mmol) with respect to 1. CHN (meas./calc.)/%: C (20.55/20.61),
H (2.33/2.31), N (7.95/8.01). EDX ratio (meas./calc.) Ge:S (1:1.49/
1:1.5). Crystallographic data for C12H16Ge4N4S6 (Mw ¼ 699.01 g/
mol): tetragonal space group I41/a,
c ¼ 21.3857(15) Å. R1 (refl.) ¼ 0.0288 (946), wR2 (refl.) ¼ 0.0432
a
¼
10.4630(4) Å,
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S. Heimann et al. / Journal of Organometallic Chemistry xxx (2016) 1e5
3
Scheme 1. Reaction scheme for the generation of 1e3. (a) Denotes the addition of 1 eq. of 1,1,3,3-tetramethyldisiloxane.
isostructural selenium homologue, [(NC(CH2)2Ge)4Se6], but here,
the extremely rapid crystallization has so far excluded the forma-
tion of crystals of sufficiently good quality. Attempts to re-
crystallize the selenide from common solvents did not yield bet-
ter single-crystals. According to a preliminary crystal structure
analysis, the selenium homologue is isostructural to 2, with all
bond lengths and angles being within the expected range. The only
remarkable difference seems to be a slight shortening of the C^N
bond, which is not discussed here into detail, as the data are not
reliable so far [17].
Compound 3 crystallizes in the triclinic space group P1 with two
formulae units in the unit cell. Besides being a rare example of
organo-functionalized tetrel tellurium complexes in general [21],
two further features are worth noting that have not been reported
for more than a few cases: 3 is an (organo)germanium telluride
clusters, and a compound that is based on a noradamantane-type
nine-atom [Tt5Ch4] cluster, which comprises a direct TteTt bond
(Tt ¼ tetrel). For long, noradamantane-type cages had been
restricted to Si/Se compounds, however, with the SieSi bond pre-
formed in the precursor. The first example of an isostructural
cluster with another elemental combination was [(RfGe)4Te5] with
Rf ¼ CH2CH2COOH or CH(CH2COOH)2 [16], making 3 the third
known Ge/Te cluster of this topology. As in the two quoted cases,
the GeeGe bond formation took place in situ under ambient con-
ditions, which has not been observed for GeeGe bonds elsewhere.
Instead, bonds between organogermanium units have always been
formed by reductive dehalogenation of according halides [22] or by
catalytic dehydrogenation of the underlying germanes [23]. In
combination with bridging chalcogen ligands, GeeGe bond for-
mation has only be reported for inorganic systems and under high
temperature conditions, as applied for the synthesis of Na8Ge4Te10
[24]. We assume that 3 was formed in a Wurtz-type coupling re-
action with Te2ꢁ acting as reductive agent (Eꢀ ¼ ꢁ1.143 V) [25] to
initially form [RfGeCl2eGeCl2Rf]. This assumption is supported by
the fact that with the weaker reductants S2ꢁ and Se2ꢁ, the bond
formation does not take place under otherwise unchanged condi-
tions. The GeeGe bond length of 2.4699(16) Å is in the range of
those observed in the quoted compounds (2.451(2) or 2.482(4) Å,
respectively).
Fig. 1. Representation of the molecular structure of 1. Ellipsoids are drawn at 50%
probability. Selected structural parameters [Å, ꢀ]: GeeCl 2.1232(7), 2.1265(4); GeeC
1.928(2), CeC 1.475(3), 1.527(4); CeN 1.141(3); CeGeeCl 110.45(8), 112.51(4); Cle-
GeeCl 106.46(3)-107.300(16); CeCeN 178.7(3).
Compound 2 crystallizes in the tetragonal space group I41/a
with four formulae units in the unit cell, depicted in Fig. 2. The
comparably short chain length of the organic substituents inhibits
intramolecular coordination of the functional group in a C^N/Sn
fashion. Consequently, the adamantane-type cluster architecture is
energetically clearly preferred with respect to the isomeric double-
decker motif. It should be noted that for Ge/S sesquichalcogenide
clusters [(RGe)4S6], even potentially back-coordinating ligands do
not cause the formation of this isomeric cluster structure, as five-
coordinated Ge atoms are disfavored due to sterical restrictions at
the ReGeS3 unit [5,15,16,19]. For this, the adamantane-type topol-
ogy forms preferably, and 2 is thus structurally closely related to the
known carboxylate-functionalized adamantane-type germanium
sesquisulfides [5,20]. However, there is a quite extraordinary high
tendency of crystallization of 2: already mechanical mixing of the
educts leads to the formation of fine colorless needles, even though
no intermolecular interactions can be deduced from the crystal
structure. We attribute this to the relatively rigid (CH2)2C^N sub-
stituent as compared to the rather flexible CMe2CH2C(O)Me group.
In the three cluster compounds (taking into consideration the
A
similar crystallization tendency was observed for the
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4
S. Heimann et al. / Journal of Organometallic Chemistry xxx (2016) 1e5
Fig. 2. Representation of the molecular structure of 2. Ellipsoids are drawn at 50% probability. Selected structural parameters [Å, ꢀ]: GeeS 2.2131(11)-2.2264(10); GeeC 1.930(4);
CeN 1.133(5); CeGeeS 104.15(11)-108.38(12); SeGeeS 111.87(3)-113.28(2); GeeSeGe 102.53(5), 103.24(5); NeCeC 179.5.
Fig. 3. Representation of the molecular structure of 3. Ellipsoids are drawn at 50%
probability. Selected structural parameters [Å, ꢀ]: GeeTe 2.5514(15)-2.5956(14); GeeC
1.955(12)-1.999(12); GeeGe 2.4699(16); CeN 1.108(17)-1.158(16); GeeTeeGe 87.84(4)-
102-03(5); CeGeeC 102.4(4)-112.1(4); TeeGeeTe 107.55(5)-116.43(5); CeCeN
177.8(14)-179.0(14).
Fig. 4. Representation of the electron density in 2, as calculated with DFT methods
(drawn between 0.05 and 0.5 a.u.).
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S. Heimann et al. / Journal of Organometallic Chemistry xxx (2016) 1e5
6595e6604.
5
preliminary structural data of the selenium homologue), the C^N
group exhibits a relatively short CeN distance (1.133(5)e1.108(17)
Å), decreasing in the direction E ¼ S/Se/Te, independent from
the underlying T/Ch unit. The distance within 2 is similar to the
CeN bond length found in aliphatic nitriles like NCeC(tBu)2C(t-
Bu)2eCN (1.139 Å) [26], while the distance that we found in 3 is
notably shorter, even shorter than reported for the olefine C2(CN)4
(1.123e1.125 Å) [27] and the cation tBueCNþePh (1.125 Å) [28]. In
the precursor compound 1 in turn, the CeN distance (1.141(3) Å)
compares well with those in organic nitriles with electron-
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withdrawing groups in
b position, such as (CH2Ph)2(F3C)CeCN
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2848e2849.
(1.42 Å) [29]. Crowded nitrile complexes, such as [(tBueCN)4Cu]þ
(CeN 1.145e1.151 Å) [30], or aromatic nitriles like C6Cl4(CN)2 (1.157,
1.160 Å) [31] or PhCN (1.186 Å) [32] possess longer CeN bonds,
which are similar to those in the free and rather unreactive (CN)e
anion (1.16 Å) [33]. When comparing these values, we assume that
the electron density within the C^N bonds of the title compounds
is comparably low, hence potentially acting as reactive dienophiles
in cycloaddition reactions for further extension of the ligand sys-
tems. Fig. 4 illustrates the delocalization of electron density over
the ligand system in 2, as calculated with density functional theory
(DFT) methods within the program system Turbomole [14]. In the
cluster core, in contrast, the electron density seems to be rather
localized.
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4. Conclusion
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1663e1666.
A nitrile functionalized trichlorogermane has been synthesized
in almost quantitative yields, which was reacted with sodium
monochalcogenides to yield the first tetragermanium hexa- or
pentachalcogenides that contain a nitrile group in the organic pe-
riphery. This provides a potentially new pathway for the generation
of functionalized core-shell compounds. Furthermore, compound 3
is a rare example of a metal-organic compound with a nor-
adamantane type topology, in particular only the third known
example with a Ge/Te elemental combination. We are currently
about to explore the chemical reactivity of the title compounds.
[16] S. Heimann, M. Holynska, S. Dehnen, Chem. Commun. 47 (2011) 1881e1883.
[17] [(NC(CH2)2Ge)4Se6] was found to be isostructural to 2, however, due to very
poor crystal quality, is has not been possible to collect a suitable crystallo-
graphic data set so far.
[18] D.R. Lide, Handbook of Chemistry and Physics, 89th edition, CRC, Paris, 2009,
p. 9.
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ꢀ
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Acknowledgement
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Financial support of this work by Deutsche For-
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Friedrich Ebert Stiftung and by the Leopoldina Nationale Akademie
der Wissenschaften is gratefully acknowledged.
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Please cite this article in press as: S. Heimann, et al., Journal of Organometallic Chemistry (2016), http://dx.doi.org/10.1016/
j.jorganchem.2016.09.011