Organobismuth(III) and dibismuthine complexes bearing N,N′- disubstituted 1,8-diaminonaphthalene ligand: Synthesis, structure, and reactivity

Article abstract of DOI:10.1021/om300758s

The organobismuth(III) and dibismuthine complexes bearing N,N′-disubstituted 1,8-diaminonaphthalene ligand were prepared. The reaction of LBiNMe₂ (1) [L = 1,8-(NSiMe₃) ₂C₁₀H₆] with ClSiMe₃

Full text of DOI:10.1021/om300758s

Article
pubs.acs.org/Organometallics
Organobismuth(III) and Dibismuthine Complexes Bearing N,N′-
Disubstituted 1,8-Diaminonaphthalene Ligand: Synthesis, Structure,
and Reactivity
Bijan Nekoueishahraki, Prinson P. Samuel, Herbert W. Roesky,* Daniel Stern, Julia Matussek,
and Dietmar Stalke*,†
†Institut fur Anorganische Chemie der Universitat Gottingen, Tammannstrasse 4, 37077 Gottingen, Germany
̈
̈
̈
̈
S
* Supporting Information
ABSTRACT: The organobismuth(III) and dibismuthine complexes
bearing N,N′-disubstituted 1,8-diaminonaphthalene ligand were prepared.
The reaction of LBiNMe2 (1) [L = 1,8-(NSiMe3)2C10H6] with ClSiMe3
results in the elimination of Me3SiNMe2, while PhCCH, Cp*H, and
PhOH proceed via HNMe2 elimination and provide the complexes of
LBiCl (2), LBiCCPh (3), LBiCp*(4), and LBiOPh (5), respectively.
Reaction of 1 with AlMe3 in n-hexane yields LBiMe (6). Compound 1
reacts with diisopropylcarbodiimide and phenyl isocyanate under
insertion at the Bi−NMe2 bond to give the addition products LBi(N-
iPr)2CNMe2 (7) and LBiN(Ph)C(O)NMe2 (8). The reactions of 1 with
sulfur and PhSiH3 result in the formation of LBi−S−BiL (9) and LBi−
BiL (10), respectively. Compounds 2−10 were characterized by
1
elemental analysis, H, 13C, and 29Si NMR spectroscopy, and X-ray
crystallographic studies.
we show that N,N′-disubstituted 1,8-diaminonaphthalene,
which is a rigid chelating ligand with delocalized π-electron
density, is suitable for the preparation and stabilization of
organobismuth(III) compounds, bismuthane with low-valent
bismuth, organobismuth chalcogenides and also of products by
insertion of the diisopropylcarbodiimide and phenyl isocyanate
groups into the bismuth−nitrogen bond.
INTRODUCTION
■
Bismuth compounds are attracting increasing attention due to
their application in heterogeneous catalysis,1 catalysts for
organic synthesis,2 superconducting materials,3 and also
biological activity.4 Bismuth amides have been used as
precursors for metal−organic chemical vapor deposition
(MOCVD) of bismuth-containing thin films due to their low
Bi−N bond energy.5 Relatively few bismuth amides with
sterically crowded substituents are known. Mason et al. have
reported the chelating tridentate triamido complex Bi[N(tBu)-
SiMe2]3CH,6 and Bertrand et al. has reported the diamido-
amine complex [MeN(CH2CH2NSiMe3)2]BiCl.7 Bismuth
complexes with chelating amidoamine and diamide ligands
have also been reported.8 An important use of organobismuth
compounds is in the preparation of dibismuthines with low-
valent bismuth.9 In addition, they also act as potential
precursors for semiconducting bismuth chalcogenides, Bi2E3
(E = chalcogen). Several well-defined organobismuth chalco-
genides such as (R2Bi)2E [R = Mes, E = O, S, Se] have been
synthesized and structurally characterized.10 The low-valent
organobismuth compounds which are very air sensitive with
weak R-Bi bonds can be synthesized in solution by reduction of
Bi(III) species with alkali metals11 or elimination of hydrogen
from secondary bismuthine R2BiH.12 In the above-mentioned
compound a bulky organic ligand has been used to stabilize the
metal center and generate Bi−Bi bonds. In our recent work we
have described the insertion of carbon−carbon and carbon−
oxygen bonds into the bismuth−nitrogen bond.13 In this paper
RESULTS AND DISCUSSION
■
Synthesis and Spectroscopic Characterization. Com-
pound [1,8-(NSiMe3)2C10H6]BiNMe2 (1) was prepared by a
previously reported method.13 The terminal NMe2 group in 1
undergoes substitution by various groups upon treatment with
appropriate reagents to afford LBiR (L = 1,8-(NSiMe3)2C10H6,
R = Cl, CCPh, Cp*, OPh, Me) type of compounds (Scheme
1). When treated with ClSiMe3 in n-hexane, 1 undergoes a
metathesis reaction in which the amide group was replaced by
chloride to afford compound 2. Organic groups can easily be
introduced in 1 by elimination of HNMe2 using acidic reagents.
Treatment of 1 with stoichiometric amounts of PhCCH,
Cp*H, and PhOH in n-hexane results in the formation of
LBiCCPh (3), LBiCp*(4), and LBiOPh (5) [L = 1,8-
(NSiMe3)2C10H6], respectively, under the elimination of
HNMe2 as shown in Scheme 1. LBiMe (6) can be synthesized
by slow addition of AlMe3 in n-hexane to the n-hexane solution
Received: August 7, 2012
Published: September 11, 2012
© 2012 American Chemical Society
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Bi−N bond. In a similar manner n-hexane solution of 1
smoothly reacts with phenyl isocyanate at room temperature to
afford crystalline 8 in 69% yield under CN insertion into the
Bi−N bond of 1. Compound 9 is obtained by reaction of 1 with
S8 in n-hexane at room temperature. Compounds 7, 8, and 9
are orange crystalline solids, which are soluble in organic
Scheme 1. Preparation of Organobismuth(III) and
Dibismuthine Complexes
1
solvents such as n-hexane, THF, and toluene. The H NMR
spectrum of 7 displays two resonances (δ 1.99, 0.34 ppm)
which can be attributed to the NMe2 and SiMe3 groups,
respectively, whereas the CH and CH3 protons of the N-
isopropyl groups resonate at 3.93 and 0.94 ppm, respectively.
1
The H NMR spectrum of 8 in C6D6 exhibits two singlets (δ
2.08, 0.31 ppm) for NMe2 and SiMe3 groups, respectively. The
13C NMR spectra of 7 and 8 show upfield-shifted resonances of
NMe2 (δ 39.7 and 37.5 ppm, respectively), in comparison to
that of 1 (δ 41.9 ppm). An attempt was made to prepare a BiH
compound by reaction of 1 with PhSiH3 which was
unsuccessful and resulted in the formation of 10 with a Bi−
Bi bond formation. Compound 10 is obtained as a red
crystalline solid which is air and moisture sensitive but stable in
the solid state under an inert atmosphere at room temperature.
1
of 1. The H NMR spectrum of each reaction mixture of
1
In the H NMR spectrum of 10, the 18 protons of the Me3Si
group resonate as a singlet (δ 0.15 ppm), and the aromatic
protons appear in the range of 7.13−7.22 ppm.
compounds 2−6 shows almost quantitative conversion of the
precursors to products, as revealed by the absence of Bi-NMe2
resonance. The H NMR spectra of compounds 2−6 in C6D6
at room temperature show singlet resonances for SiMe3 groups.
1
Molecular Structural Details. Single crystals suitable for
the X-ray structure of 2 were obtained from a mixture of n-
hexane/toluene at −30 °C, and those of 3, 4, 6, 7, 8, 9, and 10
were obtained from their saturated solutions in n-hexane at −30
°C. Crystallographic data of all compounds are furnished in
Table S1 (see Supporting Information [SI]), and important
bond parameters are listed in Tables 1 and 2. The coordination
geometry around the bismuth atom in compounds 2, 3, 4, and
6 is that of a distorted pyramidal arrangement with a
stereochemically active electron lone pair. Compound 2
1
The H NMR spectrum of 4 displays one resonance at 1.86
ppm which can be attributed to the Me protons of Cp*,
whereas the particular BiMe group in 6 resonates as a singlet at
0.43 ppm. The 13C NMR spectrum of 4 reveals two resonances
(δ 10.4, 3.3 ppm), which can be assigned to the carbon
resonances arising from SiMe3 and Bi−Cp*, respectively.
Compound 2 is a red crystalline solid which is soluble in
common organic solvents such as toluene and THF, and it is
stable in the solid state at room temperature for several months
under an inert atmosphere. Organobismuth compounds 3−6
are orange crystalline solids which are soluble in toluene, THF,
and n-hexane. All compounds are air and moisture sensitive and
hydrolyze upon exposure to air.
We have recently reported the insertion reaction of 1 with
aldehyde, ketone, alkene, and alkyne.13 Herein, we show the
reactivity of 1 toward diisopropylcarbodiimide, phenyl
isocyanate, and sulfur (Scheme 1). Reaction of diisopropylcar-
bodiimide with 1 in n-hexane results in the formation of 7,
indicating that one carbodiimide molecule is inserted into the
crystallizes in the tetragonal space group I4 with one molecule
̅
in the asymmetric unit (Figure 1). The Bi−Cl distance
(2.4784(6) Å) is shorter than those which have been reported
for complexes [2,6-(Me2NCH2)2C6H3]2BiCl (2.6086(13) Å)14
and [{HC(Et2N(CH2)2NCMe)2}BiCl2] (av 2.7055 Å)15 but is
comparable to that of a characteristic Bi−Cl covalent bond
(Σcov(Bi, Cl) 2.51 Å).16 Compounds 3 and 6 crystallize in the
monoclinic space group P21/n with two molecules in the
asymmetric unit (Figures 2, 4). The Bi−C bond length (av
2.2115 Å) in 3 is shorter than that in [tBuN-
Table 1. Selected Bond Lengths [Å] and Angles [deg] of 2, 3, 4, and 6
a
a
a
2
3
4
6
R = Cl
R = PhCC
R = Cp*
R = Me
b
Bi−R
2.4784(6)
2.1569(18)
2.127(2)
2.212(3)/2.211(3)
2.142(2)/2.162(2)
2.145(2)/2.139(2)
1.202(4)
2.62137(10)/2.59054(11)
2.1854(16)/2.1995(16)
2.1568(15)/2.1680(15)
2.249(3)/2.248(3)
2.1561(19)/2.1541(19)
2.1733(19)/2.1771(19)
Bi−N1
Bi−N2
CC
N1−Bi−N2
N1−Bi−R
N2−Bi−R
83.88
92.10(6)
95.72(6)
84.88(8)/84.48(8)
89.81/91.65(9)
83.46(6)/83.77(6)
83.69(8)/82.47(7)
93.32(9)/94.07(8)
94.75(9)/95.18(9)
b
123.53(4)/123.80(4)
b
94.91(9)/94.63(9)
118.55(4)/118.55(4)
a
b
The two numbers in this column refer to two crystallographically independent molecules in the asymmetric unit. Cp* ring centers.
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Table 2. Selected Bond Lengths [Å] and Angles [deg] of 7−
10
cmpd 7
Bi(1)−N(1)
Bi(1)−N(2)
Bi(1)−N(3)
Bi(1)−N(4)
C(17)−N(3)
C(17)−N(4)
C(17)−N(5)
2.2356(13)
2.1418(14)
2.2035(14)
2.5259(14)
1.380(2)
N(1)−Bi(1)−N(2)
N(3)−Bi(1)−N(4)
N(1)−Bi(1)−N(3)
N(1)−Bi(1)−N(4)
N(2)−Bi(1)−N(3)
N(2)−Bi(1)−N(4)
81.51
56.83(5)
91.34(5)
144.97(5)
96.87(5)
87.78(5)
1.309(2)
1.369(2)
a
cmpd 8
Bi(1)−N(1)
Bi(1)−N(2)
Bi(1)−N(3)
Bi(1)−O(1)
C(17)−N(3)
C(17)−N(4)
2.1579(14)
2.1183(14)
2.2334(15)
2.6364(13)
1.373(2)
N(1)−Bi(1)−N(2)
N(1)−Bi(1)−N(3)
N(2)−Bi(1)−N(3)
C(17)−N(3)−Bi(1)
C(17)−O(1)
85.40(6)
92.88(5)
97.08(6)
101.30(11)
1.266(2)
Figure 2. Molecular structure of 3. Anisotropic displacement
parameters are set at the 50% probability level. Only one of the two
crystallographically independent molecules is shown. H atoms are
omitted for clarity.
1.351(2)
a
cmpd 9
Bi(1)−N(1)
Bi(1)−N(2)
Bi(2)−N(3)
Bi(2)−N(4)
Bi(1)−S(1)
Bi(2)−S(1)
2.167(2)
2.138(2)
2.144(2)
2.170(2)
2.5386(7)
2.5381(7)
N(1)−Bi(1)−N(2)
N(3)−Bi(2)−N(4)
N(1)−Bi(1)−S(1)
N(2)−Bi(1)−S(1)
N(3)−Bi(2)−S(1)
N(4)−Bi(2)−S(1)
Bi(1)−S(1)−Bi(2)
Bi(1)−S(1)−Bi(2)
84.68(8)
84.00(9)
92.10(6)
95.10(6)
94.96(6)
98.22(6)
112.89(3)
113.47(3)
cmpd 10
Bi(1)−N(1)
Bi(1)−N(2)
Bi(2)−N(3)
Bi(2)−N(4)
Bi(1)−Bi(2)
2.1648(11)
2.1660(12)
2.1621(13)
2.1646(11)
3.0197(2)
N(1)−Bi(1)−N(2)
N(3)−Bi(2)−N(4)
N(1)−Bi(1)−Bi(2)
N(2)−Bi(1)−Bi(2)
N(3)−Bi(2)−Bi(1)
N(4)−Bi(2)−Bi(1)
84.51(5)
85.02(4)
89.82(6)
88.87(3)
89.95(3)
89.19(3)
Figure 3. Molecular structure of 4. Anisotropic displacement
parameters are set at the 50% probability level. Only one of the two
crystallographically independent molecules is shown. H atoms are
omitted for clarity.
a
Only one of the two crystallographically independent molecules in
the asymmetric unit.
Figure 4. Molecular structure of 6. Anisotropic displacement
parameters are set at the 50% probability level. Only one of the two
crystallographically independent molecules is shown. H atoms are
omitted for clarity.
Figure 1. Molecular structure of 2. Anisotropic displacement
parameters are set at the 50% probability level. H atoms are omitted
for clarity.
2.3638, 2.7616, 2.7745, 3.1900, 3.1998 Å) between Cp* and
bismuth resembles a scenario between an η1 and η3 mode. The
Bi−X1A (X1A = centroid of the Cp* ring) distance (2.6059 Å)
in 4 is longer than that in [(C5HR4)BiCl2]2 (R = CHMe2) (Bi−
X1A, av 2.3495 Å).18 In compounds 2, 3, 4, and 6, the Bi−N
bond lengths are in the range of 2.127(2) (in 2) to 2.1995(16)
Å (in 4) and the N−Bi−N angles span from 82.47(7) (in 6) to
84.88(8)° (in 3), which are comparable to those observed in
our previously reported compounds.13
(CH2C6H4)2BiCCPh] (2.289(4) Å).17 The Bi−Me distance in
6 (av 2.2485 Å) falls between those found in [2,6-
(Me2NCH2)2C6H3](Me)BiI (2.224(10) Å)14 and [tBuN-
(CH2C6H4)2BiMe] (2.264(6) Å).17 Compound 4 crystallizes
in the triclinic space group P1 with two molecules in the
̅
asymmetric unit (Figure 3). The Bi−C bond length pattern
with one short, two intermediate, and two longer distances (av
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The coordination geometry around the bismuth atom in
compounds 8−10 is distorted pyramidal, whereas in 7 the
bismuth atom is tetracoordinate in an irregular trigonal−
pyramidal environment. Compound 7 crystallizes in the
monoclinic space group P21/n with one molecule in the
asymmetric unit (Figure 5), while compound 8 crystallizes in
the ureato fragments are delocalized in the NC(N)O core.
Additionally, the intramolecular coordination between bismuth
and oxygen may play an important role for the stability of this
compound. Compound 9 crystallizes in the monoclinic space
group P21/n with two molecules in the asymmetric unit (Figure
7). In 9 the bismuth atoms are bound by a sulfur atom
Figure 5. Molecular structure of 7. Anisotropic displacement
parameters are set at the 50% probability level. H atoms are omitted
for clarity.
Figure 7. Molecular structure of 9. Anisotropic displacement
parameters are set at the 50% probability level. Only one of the two
crystallographically independent molecules is shown. H atoms are
omitted for clarity.
the triclinic space group P1 with two molecules in the
̅
asymmetric unit (Figure 6). The bismuth atom in 7 is
constituting a bent Bi(μ-S)Bi core with Bi−S−Bi bond angle of
av 113.18°. The bismuth−sulfur distances in 9 (av 2.5383 Å)
are similar to those in [{2-(Me2NCH2)C6H4}2Bi]2S
(2.5558(17) Å)10 and (Mes2Bi)2S (av 2.5325 Å),19 whereas
the Bi(μ-S)Bi angle of 113.18° in 9 is considerably larger when
compared with those of the latter compounds (98.17(8)°,
98.7(2)°). Two crystallographically independent molecules of 9
in the asymmetric unit are showing an intermolecular
secondary Bi−S contact with Bi3−S1 distance of 3.186 Å
(see Figure S1 in the SI). Compound LBi−BiL (10) crystallizes
in the monoclinic space group P21/c with one molecule in the
asymmetric unit (Figure 8). The N,N′-disubstituted 1,8-
Figure 6. Molecular structure of 8. Anisotropic displacement
parameters are set at the 50% probability level. Only one of the two
crystallographically independent molecules is shown. H atoms are
omitted for clarity.
coordinated to two nitrogen atoms of the anionic ligand and to
two nitrogen atoms of the carbodiimide unit. The C−N bond
distances associated with the central sp2 carbon of the
carbodiimide species are almost equal and are considerably
shorter than a typical C−N single bond, suggesting that the
three C−N bonds possess a partial double bond character
(C(17)−N(3) = 1.380(2), C(17)−N(4) = 1.309(2), and
C(17)−N(5) = 1.369(2) Å). Among these, the C(17)−N(4)
bond of 1.309(2) Å is appreciably shorter compared to the
other two bond distances. The difference in the bond lengths of
C(17)−N(3) and C(17)−N(4) is further supported by the
observation that the N(4)−Bi(1) bond (2.5259(14) Å) is
longer compared to the N(3)−Bi(1) bond (2.2035(14) Å),
indicating the weak coordinating character of the N(4)−Bi(1)
bond. In 8 both the N−C (av 1.384 and 1.352 Å) and C−O (av
1.255 Å) bond distances of the ureato fragments are in the
range of partial double bonds, indicating that the π electrons of
Figure 8. Molecular structure of 10. Anisotropic displacement
parameters are set at 50% probability level. H atoms are omitted for
clarity.
diaminonaphthalene ligands of 10 are in a trans conformation
to each other, and the N−Bi−Bi angles lie in the range of av
89.34° and av 89.57°. The Bi−Bi bond distance of 3.0197(2) Å
corresponds to a normal bismuth−bismuth single bond as
found in (Me3Si)4Bi2 (3.035(3) Å)20 or R4Bi4 (R =
(Me3Si)2CH; av 3.005 Å).21
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glass fiber, fixed to a goniometer head, and shock cooled by the crystal
cooling device.24
A notable feature of some of the bismuth compounds
reported in this contribution is their close bismuth−arene (Bi−
arene) contacts which are either intermolecular or intra-
molecular. In compound 9, each molecule in the asymmetric
unit possesses one bismuth atom that has close proximity to
one of the aromatic rings of the ligand in the same molecule,
and this leads to an intramolecular Bi−arene interaction
(Figure S2 in the SI). Moreover, one of the bismuth atoms
of one molecule interacts with the aromatic ring of the second
molecule resulting in an intermolecular Bi−arene contact. Such
weak interactions obviously have considerable influence on the
coordination environments of bismuth centers, molecular
geometries, and crystal properties. A recent work by Auer
and Mehring demonstrated the property of such Bi−arene
interactions in the triorganobismuth compound [Bi-
(CH2C6H4Cl)3]2 in which Bi−arene π-coordination and π−π
For 2 and 9, data were collected on a Bruker Apex II Ultra at 100 K
(Mo Kα radiation, λ = 71.073 pm; multilayer mirror optics), and for 3,
6, 7, 8, and 10 data were collected on a Bruker APEX II Quazar at 100
K (Mo Kα radiation, λ = 71.073 pm; multilayer mirror optics).25 The
data were integrated with SAINT,26 and a semi-empirical absorption
correction from equivalents was applied.27 The structures were solved
by direct methods (SHELXS) and refined on F2 using the full-matrix
least-squares methods of SHELXL.28 All non-hydrogen atoms were
refined with anisotropic displacement parameters. All hydrogen atoms
bonded to sp2 (sp3) carbon atoms were assigned ideal positions and
refined using a riding model with Uiso constrained to 1.2 (1.5) times
the Ueq value of the parent carbon atom. Crystallographic data
(excluding structure factors) have been deposited with the Cambridge
Crystallographic Data Centre; the CCDC numbers are listed in Table
S1 in the SI.
Preparation of [1,8-(NSiMe3)2C10H6]BiCl (2). To a stirred
solution of 1 (0.7 g, 1.26 mmol) in n-hexane (30 mL) was added
0.16 mL (1.26 mmol) of ClSiMe3 at −10 °C. The reaction mixture was
warmed to room temperature and stirred overnight. All volatiles were
removed in vacuo, and the resulting solid was washed with cold n-
hexane (20 mL) to give a red crystalline solid. The product was
recrystallized from a toluene/n-hexane mixture (2:1) to yield red
stacking interactions with distances of 3.659 Å (Bi−arenecentroid
)
and 3.869 Å (arene centroids) were observed.22 In compound
9, Bi1, Bi3, and Bi4 are at a distance of 3.173, 3.454, and 3.220
Å, respectively, from the centroids of the arene rings with which
they interact. Therefore it is expected that Bi−arene
interactions present in this compound have similar properties
of Bi−arene π-coordination as demonstrated by Auer and
Mehring. Compounds 2, 3, and 6 also exhibit weak
intermolecular Bi−arene interactions, and these are demon-
strated in Figures S3, S4, and S5, respectively (see the SI).
1
crystals. Yield: 0.47 g (69%); mp 163 °C. H NMR (500.13 MHz,
C6D6): δ 7.41 (d 2H), 7.28 (t, 2H), 7.16 (d 2H), 0.17(s, 18H). 13C
NMR (125.8 MHz, C6D6): δ 146.53, 138, 131.7, 126.8, 121.1, 116.3,
2.65. 29Si NMR (59.6 MHz, C6D6): δ 4.6. Anal. Calcd for
C16H24BiClN2Si2: C, 35.26; H, 4.44; N, 5.14. Found: C, 34.92; H,
4.21; N 5.09.
CONCLUSION
Preparation of [1,8-(NSiMe3)2C10H6]BiCCPh (3). To a stirred
solution of 1 (0.7 g, 1.26 mmol) in n-hexane (30 mL) was added 0.14
mL (1.26 mmol) of phenyl acetylene at −10 °C. The reaction mixture
was warmed to room temperature and stirred overnight. Then the
mixture was concentrated and stored at −30 °C in a freezer. Orange
crystals were obtained after two days. Yield: 0.41 g (54%); mp 98 °C.
1H NMR (500.13 MHz, C6D6): δ 7.48−7.51 (m, 2H), 7.24−7.31 (m,
3H), 6.85−6.89 (m, 2H), 6.74−6.77 (m, 3H), 0.23 (s, 18H). 13C
NMR (125.8 MHz, C6D6): δ 150.1, 138, 134, 131.9, 126.4, 123.7,
120.6, 116.2, 111.9, 3.1. 29Si NMR (59.6 MHz, C6D6): δ 4.1. Anal.
Calcd for C24H29BiN2Si2: C, 47.2; H, 4.79; N, 4.59. Found: C, 46.66;
H, 4.80; N, 4.42.
■
Organobismuth(III) and dibismuthine complexes bearing the
N,N′-disubstituted 1,8-diaminonaphthalene ligand were synthe-
sized and structurally characterized. Reaction of LBiNMe2 (1)
[L = 1,8-(NSiMe3)2C10H6] with ClSiMe3, PhCCH, Cp*H, and
PhOH in n-hexane resulted in the formation of LBiCl (2),
LBiCCPh (3), LBiCp* (4), and LBiOPh (5), respectively.
LBiNMe2 reacts with AlMe3 in n-hexane to afford LBiMe (6).
The treatment of LBiNMe2 with diisopropylcarbodiimide and
phenyl isocyanate resulted in the insertion reactions at the Bi−
NMe2 bond of 1 to afford the addition products LBi(N-
iPr)2CNMe2 (7) and LBiN(Ph)C(O)NMe2 (8), respectively.
In the reaction of 1 with sulfur, LBi−S−BiL (9) was produced.
When PhSiH3 was treated with LBiNMe2, elimination of
HNMe2 occurred to give LBi−BiL (10).
Preparation of [1,8-(NSiMe3)2C10H6]BiCp* (4). The n-hexane
solution (30 mL) of 1 (0.28 g, 0.5 mmol) was added to an n-hexane
solution (20 mL) of Cp*H (0.07 g, 0.5 mmol) at room temperature.
The reaction mixture was stirred overnight, then concentrated and
stored at −30 °C in a freezer to obtain orange crystals. Yield: 0.22 g
1
(68%); mp 148 °C. H NMR (500.13 MHz, C6D6): δ 7.23−7.41 (m,
6H), 1.86 (s, 315H), 0.27 (s, 18H). 13C NMR (125.8 MHz, C6D6): δ
148.8, 138.9, 130.3, 127.8, 126.6, 124.5, 120.3, 117.7, 10.4, 3.3. 29Si
NMR (59.6 MHz, C6D6): δ 1.14. Anal. Calcd for C26H39BiN2Si2: C,
48.43; H, 6.10; N, 4.34. Found: C, 47.94; H, 5.98; N, 4.45.
EXPERIMENTAL SECTION
■
General Comments. All experimental manipulations were carried
out under an atmosphere of dry nitrogen using standard Schlenk
techniques. The samples for spectral measurements were prepared in a
glovebox. The solvents were purified according to conventional
procedures and were freshly distilled prior to use. PhCCH, ClSiMe3,
PhSiH3, N,N′-diisopropylcarbodiimide, and phenylisocyanate were
purchased from Aldrich. NMR spectra were recorded either on a
Bruker Avance DPX 200 or Bruker Avance DRX 500 NMR
spectrometer and were referenced to the deuterated solvent in the
case of the 1H and 13C NMR spectra. 29Si NMR spectra were
referenced to SiMe4. All NMR measurements were carried out at room
temperature. Melting points were measured in sealed glass tubes on a
Preparation of [1,8-(NSiMe3)2C10H6]BiOPh (5). n-Hexane (40
mL) was added to the mixture of 1 (0.7 g, 1.26 mmol) and phenol
(0.12 g, 1.26 mmol) at room temperature and stirred overnight. After
filtration the resulting solution was concentrated and stored at −30 °C
in a freezer to obtain a yellow solid. Yield: 0.48 g (64%); mp 149 °C.
1H NMR (500.13 MHz, C6D6): δ 7.41 (d, 2H), 7.24 (t, 2H), 6.94−
7.02 (m, 4H), 6.65 (t, 1H), 6.29 (d, 2H), 0.11 (s, 18H). 13C NMR
(125.8 MHz, C6D6): δ 159.2, 146.5, 138.2, 130.5, 126.7, 122.1, 120.8,
120.5, 117.1, 2.4. 29Si NMR (59.6 MHz, C6D6): δ 3.11. Anal. Calcd for
C22H29BiN2OSi2: C, 43.85; H, 4.85; N, 4.65. Found: C, 43.65; H, 4.91;
N, 4.65.
Buchi B-540 melting point apparatus and are uncorrected. Elemental
analyses were performed at the Analytical Laboratory of the Institute
̈
of Inorganic Chemistry at Gottingen, Germany. [1,8-(NSiMe ) -
Preparation of [1,8-(NSiMe3)2C10H6]BiMe (6). AlMe3 (0.8 mL,
1.6 mmol, 2.0 M in n-hexane) was added to an n-hexane (50 mL)
solution of 1 (0.88 g, 1.6 mmol) at −78 °C. The mixture was stirred
for 1 h at this temperature and then was allowed to attain room
temperature, and stirring was continued for 12 h. The mixture was
concentrated and stored at −30 °C in a freezer to give a yellow
microcrystalline solid. Yield: 0.31 g (37%); mp 109 °C. 1H NMR
̈
3
2
C10H6]BiNMe2 (1) was prepared according to literature procedure.13
For X-ray structure analysis single crystals were selected from the
Schlenk flasks under an argon atmosphere and covered with
perfluorinated polyether oil on a microscope slide, which was cooled
with a nitrogen gas flow using the X-TEMP2.23 An appropriate crystal
was selected using a polarizing microscope, mounted on the tip of a
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Organometallics
Article
(500.13 MHz, C6D6): δ 7.23−7.31 (m, 4H), 7.44−7.48 (m, 2H), 0.43
(s, 3H), 0.28 (s, 18H). 13C NMR (125.8 MHz, C6D6): δ 149.2, 138.4,
131.2, 126.2, 120.7, 117.9, 3.3, −9.6. 29Si NMR (59.6 MHz, C6D6): δ
3.7. Anal. Calcd for C17H27BiN2Si2: C, 38.92; H, 5.19; N, 5.34. Found:
C, 38.75; H, 5.11; N, 5.46.
ACKNOWLEDGMENTS
■
Support of the Deutsche Forschungsgemeinschaft is highly
acknowledged.
Preparation of [1,8-(NSiMe3)2C10H6]Bi(NiPr)2CNMe2 (7). To a
stirred solution of N,N′-diisopropylcarbodiimide (0.1 g, 0.79 mmol) in
n-hexane (20 mL) was added a solution of 1 (0.42 g, 0.76 mmol) in n-
hexane (20 mL). The reaction was allowed to stir at room temperature
for 12 h. Then the mixture was concentrated and stored at −30 °C in a
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freezer to obtain yellow crystals. Yield: 0.4 g (78%); mp 116 °C. H
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6.97−7.03 (m, 2H), 6.84−6.91 (m, 2H), 6.59−6.66 (m, 1H), 6.18−
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mL) was added to the mixture of 1 (0.41 g, 0.75 mmol) and sulfur
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2H), 0.18 (s, 36H). 13C NMR (125.8 MHz, C6D6): δ 149.3, 144.5,
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* Supporting Information
CIF files and a table giving crystal data and details of the
structure solution and refinement for 2, 3, 4, 6, 7, 8, 9, and 10.
This material is available free of charge via the Internet at
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Corresponding Author
̈
*hroesky@gwdg.de (H.W.R); dstalke@chemie.uni-goettingen.
de (D.S)
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The authors declare no competing financial interest.
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