Ligand-protected strain-free diarylgermylenes

Article abstract of DOI:10.1021/om000743t

Reaction of 2 molar equiv of 2,6-di(1′-naphthyl)phenyllithium with bis[bis(trimethylsilyl)-amino]germylene afforded the red, crystalline, stable bis[2,6-bis(1-naphthyl)phenyl]germylene [(bisap)₂Ge, 6] in good yield. The structure of the solvate

Full text of DOI:10.1021/om000743t

418
Organometallics 2001, 20, 418-423
Liga n d -P r otected Str a in -F r ee Dia r ylger m ylen es†
Gerald L. Wegner, Raphael J . F. Berger, Annette Schier, and
Hubert Schmidbaur*
Anorganisch-chemisches Institut, Technische Universita¨t Mu¨nchen, Lichtenbergstrasse 4,
D-85747 Garching, Germany
Received August 24, 2000
Reaction of 2 molar equiv of 2,6-di(1′-naphthyl)phenyllithium with bis[bis(trimethylsilyl)-
amino]germylene afforded the red, crystalline, stable bis[2,6-bis(1-naphthyl)phenyl]germylene
[(bisap)2Ge, 6] in good yield. The structure of the solvate 6‚C6H6 was determined by single-
crystal X-ray methods. The molecule features a largely strain-free conformation with a
C-Ge-C angle of 102.72(9)° and Ge-C distances of 2.036(2) and 2.030(2) Å. These
parameters are very close to those calculated for the diphenylgermylene prototype by ab
initio methods [101.6°; 2.006 Å]. The two new wing-like 2,6-di(1-naphthyl)phenyl substituents
appear to protect the germylene center of 6 in a very efficient way without inducing
destabilizing distortions. Bis[2,4,6-triphenylphenyl]germylene [(triph)2Ge, 1] was also
prepared. Germylenes 1 and 6 were oxidized to yellow products of the composition (triph)2GeO
(2) and (bisap)2GeO (7), respectively. The compounds have been characterized by their mass
spectra, which show the parent ions in full accordance with the proposed formulas.
In tr od u ction
pound was found to be a monomer only in the gas phase
and in solution,8 but forms a dimer in the solid state.9
Further increase of the steric crowding by using one tris-
(trimethylsilyl)methyl group finally afforded a stable
germylene, [(Me3Si)3C]Ge[CH(SiMe3)2], which is mon-
omeric in all three states of aggregation.4a
There is currently widespread interest in the chem-
istry of carbenes CR2 and their heavy-atom homologues,
the silylenes SiR2 and germylenes GeR2, stannylenes
SnR2, and plumbylenes PbR2. Recent reviews1 reflect
the advances in these topical areas of research. In the
context of our studies of the preparation and reactivity
of germanium hydrides2a,d-f and low-valent germanium
compounds2b,c we became interested in stable diorgano-
germylenes R2Ge as substrates for oxidation, addition,
and insertion reactions.
A literature search revealed that only very few
diorganogermylenes have been isolated and structurally
characterized.3-7 The first stable dialkylgermylene R2-
Ge reported in 1976 appears to be bis[bis(trimethylsilyl)-
methyl]germanium,3 [(Me3Si)2CH]2Ge, but this com-
Three stable diarylgermylenes Ar2Ge were isolated
with Ar ) 2,4,6-(CF3)3C6H2; 2,4,6-(Me3C)3C6H2; 2,6-
(2,4,6-Me3C6H2)2C6H3. According to the crystal structure
analysis, the tris(trifluoromethyl)phenyl compound fea-
tures an intramolecular stabilization through short
F-Ge contacts.5 In the tris(tert-butyl)phenyl (“super-
mesityl”) compound there is structural evidence for
considerable strain.6 The two aryl groups are inequiva-
lent (C-Ge-C 108°) and show significant distortions
of the aryl rings. This leads to considerable instability
and to facile intramolecular insertion of the germylene
unit into one of the C-H bonds. Similar strain is
discernible in the 2,6-bis(mesityl)phenyl compound,
where the C-Ge-C angle is widened to 114°, the largest
value detected in diorganogermylenes, to allow phenyl
stacking.7 An unsymmetrical diarylgermylene with
2,4,6-tris(trimethylsilyl)phenyl and 2,4,6-tri(isopropyl)-
phenyl groups was also prepared, but its structure is
unknown.10
† Dedicated to Professor Herbert Schumann on the occasion of his
65th birthday.
(1) (a) Neumann, W. P. Chem. Rev. 1991, 91, 311. (b) Weidenbruch,
M. Eur. J . Inorg. Chem. 1999, 373.
(2) (a) Riedmiller, F.; Wegner, G. L.; J ockisch, A.; Schmidbaur, H.
Organometallics 1999, 18, 4317. (b) Wegner, G. L.; J ockisch, A.;
Schmidbaur, H. Z. Naturforsch. 1998, 53b, 438. (c) Tripathi, U. M.;
Wegner, G. L.; Schier, A.; J ockisch, A.; Schmidbaur, H. Z. Naturforsch.
1998, 53b, 939. (d) Schmidbaur, H.; Rott, J . Z. Naturforsch. 1980, 45b,
961. (e) Schmidbaur, H.; Rott, J .; Z. Naturforsch. 1979, 44b, 285. (f)
Schmidbaur, H.; Rott, J .; Reber, G.; Mu¨ller, G. Z. Naturforsch. 1988,
43b, 727.
(3) (a) Goldberg, D. E.; Harris, D. H.; Lappert, M. F.; Thomas, K.
M. J . Chem. Soc. Chem. Commun. 1976, 261. (b) Davidson, P. J .;
Harris, D. H.; Lappert, M. F. J . Chem. Soc., Dalton Trans. 1976, 2268.
(4) (a) J utzi, P.; Becker, A.; Stammler, H. G.; Neumann, B. Orga-
nometallics 1991, 10, 1647. (b) J utzi, P.; Becker, A.; Leue, C.; Stammler,
H. G. Neumann, B.; Hursthouse, M. B.; Karanlov, A. Organometallics
1991, 10, 3742.
(8) (a) Cowley, A. H.; Hull, S. W.; Nunn, C. M.; Power, J . M. J . Chem.
Soc., Chem. Commun. 1988, 753. (b) Lappert, M. F.; J . Power, P. P. J .
Chem. Soc., Dalton Trans. 1976, 2268. (c) Fjeldberg, T.; Haaland, A.;
Schilling, B. E. R.; Volden, H.; Lappert, M. F.; Thorne, A. J . J .
Organomet. Chem. 1985, 280, C43. (d) Fjeldberg, T.; Haaland, A.;
Schilling, B. E. R.; Lappert, M. F.; Thorne, A. J . J . Chem. Soc., Dalton
Trans. 1986, 1551.
(9) (a) Hitchcock, P. B.; Lappert, M. F.; Miles, S. J .; Thorne, A. J . J .
Chem. Soc., Chem. Commun. 1984, 481. (b) Goldberg, D. E.; Hitchcock,
P. B.; Lappert, M. F.; Thomas, K. M.; Thorne, A. J .; Fjeldberg, T.;
Haaland, A.; Schilling, B. E. R. J . Chem Soc., Dalton Trans. 1986, 2387.
(c) Trinquier, G.; Malrieu, J . P.; Rivie`re, P. J . Am. Chem. Soc. 1982,
104, 4529.
(5) Bender, J . E.; Holl, M. M. B.; Kampf, J . W. Organometallics 1997,
16, 6, 2743.
(6) (a) Lange, L.; Meyer, B.; du Mont, W.-W. J . Organomet. Chem.
1987, 329, C17. (b) J utzi, P.; Schmidt, H.; Neumann, B.; Stammler,
H.-G. Organometallics 1996, 15, 741.
(7) Simons, R. S.; Pu, L.; Olmstead, M. M.; Power, P. P. Organo-
metallics 1997, 116, 1920.
(10) Tokitoh, N.; Manmaru, K.; Okazaki, R. Organometallics 1994,
13, 167.
10.1021/om000743t CCC: $20.00 © 2001 American Chemical Society
Publication on Web 01/03/2001

Ligand-Protected Strain-Free Diarylgermylenes
Organometallics, Vol. 20, No. 3, 2001 419
In the present investigation two ligands were intro-
duced which were expected to provide sufficient shield-
ing of the germylene function to impede dimerization,
but to leave enough freedom of substituent motion to
avoid destabilizing strain at the C-Ge-C core unit. In
complementary quantum-chemical studies of the simple
model system diphenylgermylene the ground state
geometry in the gas phase of a diarylgermylene has been
calculated, to which the experimentally determined data
were to be compared.
A germylene protected in an efficient but not “inva-
sive” way should also allow the preparation of a stable
germanone of the formula R2GedO, for which there is
no precedent in the literature.
Germanones are highly elusive species, and the
literature has several reports of unsuccessful attempts
for their isolation. Simple germanones with R ) H or
Me were trapped in low-temperature argon matrixes
and identified via their vibrational absorption spectra.11
Upon warming to room temperature decomposition or
oligomerization was observed. The reaction of bis-
(supermesityl)germylene and trimethylamine oxide led
only to a germaindanol as an insertion product.6b The
product of the oxidation of {(2,4,6-tris[bis(trimethyl-
silyl)methyl]phenyl}[2,4,6-tri(isopropyl)phenyl]germyl-
ene, “(Tbt)Ge(Tip)”, using tribenzylamine oxide gave a
short-lived germanone which undergoes rearrangement
to form a germacyclobutane.12 Like many other tran-
sient germanones,13 this germanone was also identified
through its cycloaddition compounds with selected
reagents.
P r ep a r a tive Resu lts
Oxidation of the orange-red germylene 1 by trimeth-
ylamine oxide in tetrahydrofuran at 20 °C gave a yellow
solid 2, which has solubility characteristics similar to
those of the parent germylene. In the 13C NMR spec-
trum the signal of the ipso-C1 carbon atoms is shifted
to 168.8 ppm, while all other resonances are largely
unchanged. In the mass spectrum (CI) the molecular
ion [(triph)2GeO]+ appears at m/z ) 700.2, followed by
[(triph)2Ge]+, [(triph)GeO]+ (m/z ) 393.3), [(triph)Ge]+,
and [triph]+. The intensity distribution pattern is
distinctly different from the mass spectrum of the
parent germylene 1.
Single crystals of 2 could not be grown from common
solvents or their mixtures. In the IR spectrum GedO
absorptions are expected at ca. 940 cm-1 as calculated
and observed (in matrixes) for the H2GeO and Me2GeO
prototypes. For [(triph)2Ge] and [(triph)2GeO] there are
numerous ligand bands in this region, which make
reliable assignments extremely difficult. The evidence
for the germanone [(triph)2GeO] is therefore not fully
conclusive.
Bis(2,4,6-triphenylphenyl)germylene “(triph)2Ge”, 1,
was prepared by reaction of GeCl2(dioxane)14 with 2
equiv of 2,4,6-triphenylphenyllithium bis(diethyl ether)15
in diethyl ether at -60 °C. An orange-red solid product
was obtained in 88% yield. The compound is thermo-
chromic and turns yellow upon cooling to -196 °C. It is
soluble in aromatic hydrocarbons and in tetrahydrofu-
ran, but could not be crystallized from these solvents
or their mixtures with aliphatic hydrocarbons. For this
reason it was not possible to obtain a pure product. The
1H and 13C NMR spectra show complex arene multiplets
or poorly resolved resonance patterns, respectively,
which were not assigned, except for the signal due to
the ipso-C1 atoms, which appears at 162.7 ppm. In the
mass spectrum (CI) the molecular ion was observed at
m/z 683.4 followed by [(triph)Ge]+ (m/z ) 378.4) and
[triph]+ (m/z 306.3).
(11) (a) Withnall, R.; Andrews, R. J . Phys. Chem. 1990, 94, 2351.
(b) Tokitoh, N.; Matsumoto, T.; Manmaru, K.; Okazaki, R. J . Am.
Chem. Soc. 1993, 115, 8855.
(12) Tokitoh, N.; Matsumoto, T.; Okazaki, R. Chem. Lett. 1995, 1087.
(13) (a) Satge´, J .Adv. Organomet. Chem. 1982, 21, 241. (b) Barrau,
J .; Escudie´, J .; Satge´, J . Chem. Rev. 1990, 90, 283. (c) Barrau, J .; Rima,
G.; El Amine, J .; Satge´, J . J . Chem. Res. 1985, 30. (d) Barrau, J .; Rima,
G.; Lavayssierre, H.; Dousse, G.; Satge´, J . J . Organomet. Chem. 1983,
246, 227. (e) Pfister-Guillouzo, G.; Guimon, C. Phosphorus Sulfur 1985,
23, 197.
(14) Kouvetakis, J .; Haaland, A.; Shorokhof, D. J .; Volden, H. V.;
Girichev, G. V.; Sokolov.; Schmittinger, S.; Matsunaga, P. J . Am. Chem.
Soc. 1998, 120, 6738.
There is also no fully confirmed evidence for any other
monomeric compound of the general type X2GedO, with
X other than alkyl or aryl. The determination of the
crystal structure of the compound with X ) (Me3Si)2N
has shown that the compound is a dimer with a [GeO]2
four-membered ring.16 The sulfur, selenium, and tel-
lurium analogues are also known to be dimers.17
(15) (a) Olmstead, M. M.; Power, P. P. J . Organomet. Chem. 1991,
408, 1. (b) Girolami, G. S.; Riehl, M. E.; Suslick, K. S.; Wilson, S. R.
Organometallics 1992, 11, 3907.
(16) Hitchcock, P. B.; J asim, H. A.; Lappert, M. F.; Leung, W.-P.;
Rai, A. K.; Taylor, R. E. Polyhedron 1991, 10, 1203.

420 Organometallics, Vol. 20, No. 3, 2001
Wegner et al.
extracted with pentane. Crystallization of the residue
from diethyl ether afforded a dietherate of bis[2,6-(1-
naphthyl)]germylene (6), in 32% yield. The crystal
structure of this product could not be refined to a
satisfactory level owing to disorder of one of the solvent
molecules. However, recrystallization from benzene/n-
octane gave red crystals of the diarylgermylene (6) with
1 equiv of benzene in a fully ordered structure (below).
The composition of the product was confirmed by
mass spectrometry (chemical ionization), the molecular
ion being observed in high intensity. Owing to the low
symmetry of the molecule, the compound shows no
To synthesize a pure, crystalline germylene, which
could be a more convenient starting material for oxida-
tion reactions, it was therefore necessary to design a
new ligand. This ligand was required to be amenable
neither to germylene insertion reactions nor to nucleo-
philic substitution or intramolecular rearrangement.
2,6-Bis(1-naphthyl)phenyl, “bisap”, was expected to
meet all these conditions, because it has no alkyl or
substituted alkyl substituents.
2,6-Bis(1-naphthyl)(1-iodo)benzene (4) was prepared
in 62% yield and lithiated using an equivalent quantity
of n-butyllithium in hexane/diethyl ether. 2,6-Bis(1-
naphthyl)phenyllithium was isolated as a colorless
crystalline solid (5). A solution of the latter in diethyl
ether was treated with bis[bis(trimethylsilyl)amino]-
germylene in 2:1 molar ratio at -50 °C. The reaction
mixture turned purple, and after evaporation of all
volatile components the byproduct LiN(SiMe3)2 could be
1
signal in its 73Ge NMR spectrum. However, the H and
13C NMR spectra are in full agreement with the
proposed formula. The IR spectrum is extremely rich
in absorption bands in the aromatic regions. All assign-
ments are therefore tentative.
Preliminary studies of the oxidation reactions using
nitrous oxide provided a colorless product [(bisap)2GeO]
(7), which has the expected molecular ion in the mass
spectrum (CI, m/z ) 748) with the correct isotope
pattern. More extensive investigations are under way.
Molecu la r Str u ctu r e of th e New Ger m ylen e.
Crystals of 6‚C6H6 (from benzene/n-octane at 0 °C) are
monoclinic, space group P21/n with Z ) 4 germylene and
benzene molecules in the unit cell. There are no sub-
van der Waals contacts between these components in
the lattice. The germylene should therefore be consid-
ered strictly as a monomer. The molecule 6 has no
crystallographically imposed symmetry, but the struc-
ture approaches quite closely the symmetry require-
ments of a 2-fold axis passing through the Ge atom and
(17) (a) Ellis, D.; Hitchcock, P. B.; Lappert, M. F. J . Chem. Soc.,
Dalton Trans. 1992, 3397. (b) Wegner, G. L.; J ockisch, A.; Schier, A.;
Schmidbaur, H. Z. Naturforsch. 2000, 55b, 347.

Ligand-Protected Strain-Free Diarylgermylenes
Organometallics, Vol. 20, No. 3, 2001 421
of the naphthyl-substituted phenyl groups. Obviously
rotations about the Ge-C and aryl-aryl bonds are
sufficient to accommodate these ligands.
Exp er im en ta l P a r t
Gen er a l Meth od s. The experiments were carried out under
an atmosphere of dry nitrogen using Schlenk techniques.
GeCl2‚dioxane,14 Ge[N(SiMe3)2]2,18 (Triph)Li(Et2O)2,15 and Me3-
NO19 were prepared and purified according to published
procedures. Solvents were appropriately dried, distilled, and
saturated with dry nitrogen; glassware was dried in an oven
and filled with nitrogen. All NMR spectra were recorded at
20 °C on a J EOL-J NM-LA 400 spectrometer (1H at 400.05
MHz, 13C at 100.50 MHz, 73Ge at 13.83 MHz) in sealed tubes
with predried C6D6 as solvent. Mass spectra were recorded
with a Finnigan MAT 90 mass spectrometer (chemical ioniza-
tion (CI)-MS, isobutane) and with an analytical gas-liquid-
chromatograph (GLC)-MS Hewlett-Packard 5890 Series II
(column HP1, cross-linked methylsilicone gum 12 m/0.2 mm,
thickness of film 0.33 µm) with a mass selective detector HP
MS 5971 A (electron ionization (EI)-MS 70 eV). Microanalyses
were performed in-house by combustion.
F igu r e 1. Molecular structure of (bisap)2Ge, 6, in crystals
of 6 × benzene with atomic numbering (ORTEP drawing
at the 50% probability level; H atoms omitted for clarity).
Ge-C1 2.036(2), Ge-C2 2.030(2) Å, C1-Ge-C2 102.72-
(9)°.
(Tr ip h )2Ge (1). To a solution of (triph)Li(OEt)2 (5.31 g,
11.52 mmol) in 20 mL of diethyl ether was added GeCl2‚
dioxane (1.34 g, 5.78 mmol). The reaction mixture was stirred
at -50 °C for 2 h and thereafter allowed to warm to room
temperature. After continued stirring for 6 h the volatiles were
stripped off in vacuo. The product was extracted from the
residue with 20 mL of toluene. Evaporation of the solvent gave
an orange solid. Yield: 3.86 g, 98%. 1H NMR (20 °C): 6.5-7.8
(m). 13C{1H} NMR (20 °C): 126.6, 128.6, 128.7, 128.9, 129.1,
129.2, 130.6, 132.8, 134.1, 143.1, 144.2, 162.7 (C1). MS (CI,
isobutane): m/z 683.4 [M+], 378.4 [M+ - triph], 306.3 [triph+],
229.3 [triph - Ph]. Calcd for C48H34Ge (683.39): C, 84.36; H,
5.01. Found: C, 83.38; H, 5.44.
(Tr ip h )2GeO (2). Me3NO (147 mg, 1.96 mmol) was added
to a solution of (triph)2Ge (1.34 g, 1.96 mmol) in 15 mL of THF.
The mixture was stirred at room temperature for 24 h.
Volatiles were removed in vacuo. The residue was washed with
10 mL of pentane. Extraction with 10 mL of toluene and
evaporation afforded a yellow solid (2). Yield: 1.13 g, 83%. 1H
NMR (20 °C): 6.8-7.8 (m). 13C{1H} NMR (20 °C): 125.6, 127.3,
127.5, 128.5, 129.1, 129.9, 130.0, 130.1, 141.7, 142.9, 168.8 (C1).
MS (CI, isobutane): m/z 700.6 [(triph)2GeO+], 683.4 [(triph)2-
Ge+], 393.3 [(triph)2GeO+ - Triph], 379.3 [M+ - triph], 306.4
[triph+]. Calcd for C48H34GeO (699.39) C, 82.43; H, 4.90.
Found: C, 83.14; H, 5.44%; N, 0.5. The nitrogen contents
suggest the presence of some residual Me3NO or NMe3.
2,6-Dibr om oiod oben zen e (3). The compound was pre-
pared following a literature procedure.20 It was recrystallized
twice from 2-propanol instead of benzene-ethanol. The puri-
fied product was dissolved in dry THF. The solvent and all
volatile components trapped in the crystals were removed in
vacuo. H NMR (20 °C): δ 6.12 (t, 1H, J ) 7.8 Hz, H4), 6.92
(d, 2H,3J ) 7.8 Hz, H3/5). 13C{1H} NMR (20 °C): δ 96.8 (C1),
130.1 (C4), 131.0 (C3/5), 131.5 (C2/6). MS (EI, 70 eV): m/z 362
[M+]; 235 [M+ - I]; 155 [M+ - I - Br]; 75 [M+ - I - 2Br].
Calcd for C6H3Br2I (361.8): C, 19.92; H 0.83. Found: C, 20.08;
H, 0.89.
2,6-Bis(1′-n a p h th yl)iod oben zen e, [bisa p I] (4). A suspen-
sion of magnesium chips (12 g, 0.5 mol) in 100 mL of THF
was activated with few drops of 1,2-dibromoethane. Ten
F igu r e 2. Calculated structure of Ph2Ge (arbitrary radii).
Ge-C 2.006 Å, C-Ge-C 101.6°.
bisecting the C-Ge-C angle. At only 102.72(9)° this
angle is the lowest among the data documented in the
literature except for the CF3-substituted example [99.95-
(10)°; above] with its intramolecular F-Ge contacts.
An inspection of the structure (Figure 1) shows that
the two Ge-bound phenyl groups with their four naph-
thyl substituents can be readily accommodated in the
environment of the Ge atom, suggesting a strain-free
conformation. There are no significant distortions of the
geometries of any of the arene rings and of the inter-
ring angles. The two Ge-C distances [2.036(2) and
2.030(2) Å] and the C-Ge-C angle [102.72(9)°] may
therefore be taken as the “natural” or intrinsic param-
eters of a diarylgermylene.
Qu a n tu m -Ch em ica l Ca lcu la tion s of Dip h en yl-
ger m ylen e. Ab initio calculations at the B3LYP level
of theory using standard programs gave data for diphen-
ylgermylene as a simple reference compound. The
ground state of the molecule has a structure with C2
symmetry, as shown in Figure 2. The phenyl groups
show a standard geometry. The Ge-C distances were
calculated to be at 2.006 Å, the C-Ge-C angle at 101.6°.
Both values are very close to the experimental data for
germylene 6 in support of the idea that this new
diarylgermylene has a largely strain-free geometry at
the core unit. Deviations in the torsion angles are not
unexpected and reflect the specific steric requirements
1
3
(18) (a) Harris, D. H.; Lappert, M. F. J . Chem. Soc., Chem. Commun.
1974, 895. (b) Chorley, R. W.; Hitchcock, P. B.; Lappert, M. F.; Leung,
W.-P.; Power, P. P.; Olmstead, M. M. Inorg. Chim. Acta 1992, 198,
203.
(19) Soderquist, J . A.; Anderson, C. L. Tetrahedron Lett. 1986, 27,
3961.
(20) Du, C.-J . F.; Hart, H.; Ng, K.-K. D. J . Org. Chem. 1986, 51,
3162.

422 Organometallics, Vol. 20, No. 3, 2001
Wegner et al.
F igu r e 3. (a) Molecular ion in the mass spectrum (FAB) of (bisap)2GeO (7), (b) calculated isotope pattern for C52H34GeO
(747.45).
Ta ble 1. Ca lcu la ted [B3LYP /TZV(P )] Ca r tesia n
Coor d in a tes of P h 2Ge in m -10
percent of a solution of 1-bromonaphthalene (100 g, 0.48 mol)
in tetrahydrofuran was then added, and stirring continued
until a mild exothermic reaction commenced. The addition was
slowly continued to maintain reflux of the solvent. Thereafter
the mixture was refluxed for 2 h. A solution of 2,6-dibromo-
iodobenzene (12 g, 66.3 mmol) in 100 mL of THF was added
dropwise at room temperature within a period of 2 h. After
the reaction mixture had been stirred for 4 h, iodine (95 g,
0.75 mol) was added in small portions with cooling (ice bath),
and stirring was continued overnight. A solution of Na2SO3
(28 g, 0.22 mol) in 400 mL of water was added to destroy the
excess iodine. The aqueous layer was separated and washed
twice with 100 mL of toluene. The combined organic layers
were washed with 300 mL of water and 200 mL of a saturated
aqueous NaCl. MgSO4 was used to dry the organic layer. The
solvents were evaporated after filtration. Most of the side
product 1-iodonaphthaline was removed by sublimation (150
°C/0.05 mbar). Recrystallization from a 2:1 mixture of 2-pro-
panol and toluene and finally from pure toluene afforded
colorless crystals of bisapI‚0.5 toluene. The toluene can be
removed by heating the material to 100 °C in vacuo for several
hours to afford pure 4 as a white solid. Yield: 18.76 g, 62%.
1H NMR (20 °C): 7.06-7.40 (m). 13C{1H} NMR (20 °C): 107.3
(C1), 125.5 (C8′), 126.1 (C3′), 126.1 (C6′), 126.4 (C7′), 126.5 (C4′),
127.5 (C2′), 128.4 (C5′), 128.6 (C4), 129.9 (C3/5), 132.2 (C8a′),
134.2 (C4a′), 143.7 (C1′), 147.3 (C2/6). IR (cm-1): 3044, 1593,
1554, 1507, 1391, 1383, 1010, 861, 798, 776, 737, 720, 703,
668, 618, 566, 499. MS (EI, 70 eV): m/z ) 456 [M+], 329
[M+ - I], 202 [M+ - I - Naph], 163 [M2+], 127 [Naph+]. Calcd
for C26H17I (456.32): C, 63.43; H, 3.76. Found: C, 63.36; H,
3.79.
(Bisa p )2Ge (6). With rapid stirring, 5.2 mL of a 1.6 M
solution of n-BuLi (8.3 mmol) in hexane was added dropwise
to a slurry of (bisap)I (3.8 g, 8.3 mmol) in 15 mL of diethyl
ether at room temperature. Stirring was continued for 30 min,
then the volume of the resulting yellow solution was reduced
to incipient crystallization and cooled to -35 °C overnight. The
colorless crystals obtained (5 g) were washed twice with 15
mL of pentane. A solution of Ge[N(SiMe3)2]2 (1.48 g, 3.75 mmol)
in 20 mL of diethyl ether was added at -50 °C with stirring.
The reaction mixture, which took on an intense purple color,
was allowed to warm to room temperature within 2 h and then
stirred for a further 12 h at ambient temperature. The volatile
materials were removed under reduced pressure, and the
Ge
C
C
H
C
H
C
H
C
H
C
H
C
C
H
C
H
C
H
C
H
C
H
-0.000849
1.553854
1.563631
0.654170
2.765730
2.803727
2.728498
2.716690
3.926555
4.845675
3.909621
4.814722
-1.554055
-2.770337
-2.811507
-1.558539
-0.645509
-3.930377
-4.852303
-2.722493
-2.706293
-3.907565
-4.812153
0.003112
0.030728
0.616478
1.044938
-0.487734
-0.918075
0.672194
1.141562
-0.464126
-0.885573
0.122879
0.156972
-0.031831
0.472362
0.894575
-0.606604
-1.024379
0.447433
0.860740
-0.663609
-1.123435
-0.125706
-0.162503
-1.401064
-0.134178
1.143071
1.547894
-0.621116
-1.617887
1.901716
2.878987
0.145423
-0.245380
1.407752
2.002969
-0.132921
-0.624148
-1.624248
1.149280
1.557152
0.143479
-0.249355
1.909197
2.890932
1.412066
2.007940
residue was washed twice with 15 mL of pentane to give a
dietherate, (bisap)2Ge‚2 OEt2. The remaining red powder was
recrystallized from benzene/n-octane to afford 6 as red crystals.
1
Yield: 0.97 g, 32%. H NMR (20 °C): δ 6.8-8.2 (m), 13C{1H}
NMR (20 °C): δ 125.0 (C8′), 125.2 (C6′), 125.9 (C3′), 126.4 (C7′),
126.5 (C4′), 126.8 (C2′), 127.1 (C5′), 129.8 (C4), 130.2 (C3/5), 134.2
(C8a′), 134.6 (C4a′), 143.3 (C1′), 145.0 (C2/6), 168.6 (C1). 73Ge
NMR: no signal. MS (CI): m/z 732.3 [M+], 401.1 [M+ - bisap],
330.1 [bisap+], 202.0 [bisap+ - Naph]. IR (cm-1): 3049, 1652,
1617, 1593, 1554, 1507, 1390, 907, 864, 798, 788, 776, 734,
636, 617, 568, 499. Calcd for 6‚C6H6, C58H40Ge (809.5) C, 86.05;
H 4.98. Found: C, 87.25; H, 4.89.
(Bisa p )2GeO (7). (Bisap)2Ge‚2OEt2 (0.6 g, 0.69 mmol) was
dissolved in 3.5 mL of toluene in a 50 mL flask, and the
headspace was filled with 45 mL of dry N2O (20.3 mmol). The
flask was kept at 0 °C for 2 days. The red solution was
discolored, and a small amount of a precipitate formed.
Evaporation of the solvent in vacuo left 0.51 g of a white
powder (98% yield). The mass spectrum is shown in Figure 3.
Attempts to obtain this product completely free of solvent and
to recrystallize it have not yet been successful.

Ligand-Protected Strain-Free Diarylgermylenes
Organometallics, Vol. 20, No. 3, 2001 423
Cr ysta l Str u ctu r e of Com p ou n d 6‚C6H6. The data were
collected on a Nonius DIP2020 image plate system using
graphite-monochromated Mo KR radiation. The structure was
solved by a combination of direct methods and difference
Fourier syntheses and refined by full matrix least-squares
calculations on F2. The thermal motion was treated anisotro-
pically for all non-hydrogen atoms. Hydrogen atoms were
calculated and allowed to ride on their corresponding C atoms
with fixed isotropic contributions. Crystal data for C58H40Ge:
Mr ) 809.49, dark red crystals, monoclinic, a ) 15.901(1), b )
15.175(1), c ) 18.335(1) Å, â ) 112.96(1)°, space group P21/n,
Z ) 4, V ) 4073.6(4) Å3, Fcalc ) 1.320 g cm-3, F(000) ) 1680;
T ) -130 °C; 9717 measured and unique reflections; 532
refined parameters, wR2 ) 0.1025, R ) 0.0574 for 8064
reflections [Fo g 4σ(Fo)] used for refinement. Residual electron
densities: +0.51/-0.61 e/Å3. The function minimized was
three-parameter hybrid-functional in conjunction with the
correlation functional according to Lee, Yang, and Parr23 was
chosen as a suitable level of theory (B3LYP). As basis functions
the triple-ú split-valence set augmented with polarization
functions on Ge and C was used [TZV(P)].24
The structure was optimized without any constraints re-
garding symmetry, and in order to prove the calculated
geometry as a local minimum on the energy hypersurface a
frequency analysis was carried out.
Ack n ow led gm en t. This work was supported by
Fonds der Chemischen Industrie. The authors wish to
thank Professor P. Pyykko¨, University of Helsinki, for
making computational facilities available, and Dr. G.
Rabe for the donation of (triph)Br.
wR2 ) {∑[w(Fo - Fc2)2]/∑[w(Fo2)2]}1/2; w ) 1/[∑2(Fo2) +
2
Su p p or tin g In for m a tion Ava ila ble: Details of crystal
data, data collection, and structure refinement and tables of
atomic coordinates, isotropic and anisotropic thermal param-
eters, and all bond lengths and angles. This material is
available free of charge via the Internet at http://pubs.acs.org.
(ap)2 + bp]; p ) (Fo2+ 2Fc2)/3; a ) 0.0264, b ) 5.00. Important
interatomic distances and angles are given in the Figure 1
caption. Anisotropic thermal parameters and complete lists
of interatomic distances and angles have been deposited with
the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK. The data are available on request
on quoting CCDC-148625.
OM000743T
Com p u ta tion a l Deta ils. The structure of the Ph2Ge
molecule was calculated with the Turbomole21 program pack-
age (version V5.2). Turbomole’s implementation22 of the Becke
(22) (a) Eichkorn, K.; Treutler, O.; O¨ hm, H.; Ha¨ser, M.; Ahlrichs,
R. Chem. Phys. Lett. 1995, 242, 652. (b) Eichkorn, K.; Weigend, F.;
Treutler, O.; Ahlrichs, R. Theor. Chem. Acc. 1997, 97, 119.
(23) (a) Becke, A. D. J . Chem. Phys. 1993, 98, 5648. (b) Lee, C.; Yang,
W.; Parr, R. G. Phys. Rev. 1988, B37, 785.
(21) Ahlrichs, R.; Ba¨r, M.; Ha¨ser, M.; Horn, H.; Ko¨mel, C. Chem.
Phys. Lett. 1989, 162, 165-169.
(24) Scha¨fer, A.; Huber, C.; Ahlrichs, R. J . Chem. Phys. 1994, 100,
5829.