Arenechromiumtricarbonyl complexes of silyl(germyl)(stannyl)- and silyl(germyl)(plumbyl)methanes including the unexpected formation of arenechromiumtricarbonyldimethylsilanol, (η6-C6H5)Cr(CO)3SiMe2OH

Article abstract of DOI:10.1016/j.jorganchem.2010.01.027

Treatment of PhMe₂SiCH₂GeMe₃ (1) with t-BuLi followed by addition of Me₃ECl, E = Sn, Pb, results in the formation of phenylsilyl(germyl)stannyl- and phenylsilyl(germyl)plumbyl-methanes, PhMe₂Si(Me₃Ge)(EMe₃)CH, E = Sn (2), Pb (3). The thermal reaction of 1, 2 and 3 with Cr(CO)₆ yields the corresponding aryl-Cr(CO)₃ analogs, {(η⁶-C₆H₅)Cr(CO)₃}Me₂Si(Me₃Ge)CH₂ (4) and {(η⁶-C₆H₅)Cr(CO)₃}Me₂Si(Me₃Ge)(EMe₃)CH, E = Sn (5), Pb (6). The thermal treatment of 2 with Cr(CO)₆ in a wet THF/di-n-butyl ether mixture results in the formation of the arenechromiumtricarbonyl silanol {(η⁶-C₆H₅)Cr(CO)₃}Me₂SiOH (7) which exhibits amphiphilic character, forming H-bonded chains in the solid state in a head-to-head arrangement of the areneCr(CO)₃ units.

Full text of DOI:10.1016/j.jorganchem.2010.01.027

Journal of Organometallic Chemistry 695 (2010) 1168–1174
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Arenechromiumtricarbonyl complexes of silyl(germyl)(stannyl)
- and silyl(germyl)(plumbyl)methanes including the unexpected formation
of arenechromiumtricarbonyldimethylsilanol, (
g
6-C6H5)Cr(CO)3SiMe2OH
*
*
Hemant K. Sharma , Francisco Cervantes-Lee, Keith H. Pannell
Department of Chemistry, University of Texas at El Paso, El Paso, TX 79968-0513, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
Treatment of PhMe2SiCH2GeMe3 (1) with t-BuLi followed by addition of Me3ECl, E = Sn, Pb, results in the
formation of phenylsilyl(germyl)stannyl- and phenylsilyl(germyl)plumbyl-methanes, PhMe2Si(Me3-
Ge)(EMe3)CH, E = Sn (2), Pb (3). The thermal reaction of 1, 2 and 3 with Cr(CO)6 yields the corresponding
Received 2 December 2009
Received in revised form 20 January 2010
Accepted 21 January 2010
Available online 29 January 2010
aryl-Cr(CO)3 analogs, {(
Me3)CH, E = Sn (5), Pb (6). The thermal treatment of 2 with Cr(CO)6 in a wet THF/di-n-butyl ether mixture
results in the formation of the arenechromiumtricarbonyl silanol {(
6-C6H5)Cr(CO)3}Me2SiOH (7) which
g g
6-C6H5)Cr(CO)3}Me2Si(Me3Ge)CH2 (4) and {( 6-C6H5)Cr(CO)3}Me2Si(Me3Ge)(E-
g
Keywords:
exhibits amphiphilic character, forming H-bonded chains in the solid state in a head-to-head arrange-
ment of the areneCr(CO)3 units.
Group 14 methanes
Arenechromiumtricarbonyl complexes
Silanol
Ó 2010 Elsevier B.V. All rights reserved.
1. Introduction
quent quenching with Me3ECl (E = Sn, Pb) resulted in mixed-tri-
substituted methanes, (PhMe2Si)(Me3Ge)(Me3E)CH (E = Sn, Pb)
Di- and trisubstituted Group 14 homoleptic methyl groups,
R2CH and R3C, R = R03Si, R03Ge, R03Sn, are routinely used as stabiliz-
ing groups to isolate kinetically labile methylenes and dimetal-
lenes of Group 14 elements [1,2]. They are also versatile reagents
in synthetic chemistry [3,4] and for example, functionalized allylic
silanes have been synthesized in high yield from the reaction of
tris(trimethylsilyl)methyl borane (Me3Si)3CBH2 with alkenyl lith-
ium reagent [4]. However, related heteroleptic systems with differ-
ing group 14 groups have received only scant attention [5–7]. We
and Shimizu group reported the synthesis of mixed group 14
methanes, (Me3Si)(Me3Ge)(Me3Sn)CH [5,6]. In continuation of such
studies, we report the synthesis and characterization of arenechro-
miumtricarbonyl complexes of the mixed group 14 methanes,
(PhMe2Si)(Me3Ge)(Me3E)CH (E = Sn, Pb). A crystal structure of the
(E = Sn (2); Pb (3)) after hydrolytic workup in 72% and 40% yields
respectively, as colorless oils. If the metallation reaction is per-
formed with n-BuLi, only poor yields of 2 and 3 were obtained.
The new compounds were characterized by NMR spectroscopy, Ta-
ble 1. The 1H and 13C NMR of 2 and 3 exhibited two resonances for
the diastereotopic methyl protons and carbons of the SiMe2
groups. The related 119Sn NMR and 207Pb NMR were significantly
shifted to low field compared to Me4Sn and Me4Pb, i.e. 14 ppm
and 63 ppm, respectively.
The thermal reactions of 1, 2 and 3 with Cr(CO)6 in a refluxing
7:1 di-n-butylether/THF solvent mixture resulted in the formation
of yellow crystalline chromium tricarbonyl complexes, 4, 5 and 6 in
moderate yields, Eq. (1).
The yellow complexes slowly oxidize in the solid state, whereas
in solution the decomposition is more rapid; their spectral and
analytical data are reported in the experimental section. As ex-
pected the NMR spectra of the chromium complexes 4-6 exhibited
an upfield displacement of chemical shifts of the aromatic protons
and carbons of ꢁ 2 ppm and ꢁ 30–40 ppm, respectively [8,9]. No
significant change in the chemical shifts for the 119Sn and 207Pb
resonances of the arenechromiumtricarbonyl complexes 5 and 6
were observed compared to those of the precursors 2 and 3.
Our attempts to deprotonate complex 5 with LDA (lithium
diisopropamide) and subsequent quenching with Me3PbBr which
would have allowed access to arenechromiumtricarbonyl methane
with four different group 14 elements, catorcane molecule [5],
have not, thus far, been successful.
silanol, (
g
6-C6H5)Cr(CO)3SiMe2OH, obtained from the thermal
6-C6H5)Me2Si}(Me3Ge)(Me3Sn)CH with Cr(CO)6 in
reaction of {(
g
wet THF/butyl ether mixture, is also reported.
2. Results and discussion
Treatment of phenyldimethylsilyl(trimethylgermyl)methane,
PhMe2SiCH2GeMe3, (1) with t-BuLi in a 4:1 THF/HMPA mixture
at ꢀ78 °C led to the formation of [PhMe2SiCHGeMe3]ꢀLi+. Subse-
* Corresponding authors. Tel.: +1 915 747 7565; fax: +1 915 747 5748 (H.K.S.).
E-mail addresses: hsharma@utep.edu (H.K. Sharma), kpannell@utep.edu (K.H.
Pannell).
0022-328X/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.01.027

H.K. Sharma et al. / Journal of Organometallic Chemistry 695 (2010) 1168–1174
1169
SiMe2Ph
H
Me
Si
Me
H
butyl ether / THF
Cr(CO)6
+
+ 3 CO
H
GeMe3
H
Cr
GeMe3
C
C
O
C
O
O
4
SiMe2Ph
H
Me
Si
ð1Þ
Me
EMe3
butyl ether / THF
Cr(CO)6
+
+ 3 CO
Me3E
GeMe3
H
Cr
GeMe3
C
C
O
C
O
O
(E = Sn (2); Pb = (3))
(E =Sn (5); Pb (6))
2.1. Hydrolysis reaction
Me3SnCH2EMe3 (E = Si, Ge) by electrophiles and acids under mild
conditions has been described previously [10]. The Me3E group ap-
pears to activate the Sn–CH2 toward such reactions, thus in our
system the presence of water can be expected to result in such
Sn–CH bond cleavage. The cleavage of the Si–CH2 bond in the
Me3SnCH2SiMe3 was not observed [10] and suggests that the
equivalent bond in our system, Si–CH, is activated by the presence
Thermal treatment of 2 with Cr(CO)6, in a wet n-butyl ether/THF
solvent mixture at 140 °C for three days produced the unexpected
arenechromiumtricarbonyl silanol 7 as well as complex 4 in an
approximately 1:2 ratio, Eq. (2).
of the (g
6-C6H5)Cr(CO)3) group. The fact that there appears to be
SiMe2Ph
no Ge–CH cleavage supports this suggestion and is currently being
tested. It is well documented that the benzylic carbon is activated
by the chromiumtricarbonyl species to produce stable benzylic
cations [11]. The electrochemical studies of the (organosilyl)arene-
chromium tricarbonyl complexes also suggests the stability of the
H
Me3Sn
GeMe3
oxidized
(organosilyl)arenechromiumtricarbonyl
compounds
butyl ether/wet THF
Me
Cr(CO)6
which is solvent and substituent depended [12].
Me
Si
H
2.2. X-ray structure of {(g6 -C6H5)Cr(CO)3}Me2SiOH (7)
SiMe2OH
H
The structure of compound 7, Fig. 1, exhibits the classical g6
arene-ML3 form of a piano stool with a planar benzene ring seat ly-
ing symmetrically above the -bonded chromium atom with the
three carbonyl groups oriented in a tripod fashion in opposite
direction to the benzene ring [8,9]. The structural parameters
and selected bond angles and distances are provided in Tables 2
and 3. The torsion angles Cipso-ring centroid–Cr–Cn(O) (n = 7, 8
and 9 in Fig. 1) are ꢀ168.40, +72.60 and ꢀ50.95 degrees respec-
tively, the tripodal arrangement is about 12° from the ideally
eclipsed conformation (torsion angles ꢀ60, +60 and +180 degrees)
relative to the para and two ortho carbon atoms in the ring.
-
Cr
+
Cr
GeMe3
C
C
p
C
C
O
C
O
O
C
O
O
O
4
7
ð2Þ
Presumably, product 7 derives from the hydrolytic cleavage of the
Si–CH bond at high temperature, a reaction that would also produce
Me3SnCH2GeMe3. Indeed the NMR spectral analysis of the liquid ob-
tained after removing the butyl ether did exhibit the expected 119Sn
resonance at 13.3 ppm assigned to Me3SnCH2GeMe3 [7e]. Complex
7 was characterized by NMR spectroscopy and recrystallization
from toluene afforded yellow crystals suitable for X-ray crystallog-
raphy, vide infra.
In addition to the cleavage of the Si–CH bond, there is signifi-
cant cleavage of the Sn–CH bond to produce the chromium
complex 4, i.e. we obtained two unexpected arenechromiumtricar-
bonyl products at the same time, without formation of the ex-
pected product 5. It is not, however, clear at this time whether
the cleavage reactions occur prior to, or subsequent to, chromium-
tricarbonyl complexation. The cleavage of the Sn–CH2 bond in
Table 1
Selected 29Si, 119Sn and 207Pb NMR shifts (d ppm) for 1-6.
Compd
29Si
119Sn
207Pb
1
2
3
4
5
6
ꢀ2.98
ꢀ1.72
ꢀ0.56
1.13
14.1
63.2
59.3
2.29
12.5
3.45

1170
H.K. Sharma et al. / Journal of Organometallic Chemistry 695 (2010) 1168–1174
Fig. 1. Molecular structure of 7. Thermal ellipsoids set at 50% of probability, only one position for the disordered hydroxyl hydrogen is shown.
Table 2
Table 3
Structure determination summary of 7.
Selected bond lengths (Å) and angles (°) for 7.
Empirical formula
C11H12CrO4Si
Cr–C1
Cr–C9
Si–C10
Si–C1
C1–C6
C2–C3
C4-C5
2.2204(19)
1.857(2)
1.848(2)
1.878(2)
1.429(3)
1.404(3)
1.412(3)
Cr–C4
Si–O4
Si–C11
O3–C9
C1–C2
C3–C4
C5–C6
2.2074(19)
1.6518(14)
1.853(2)
1.149(3)
1.421(3)
1.402(3)
1.402(3)
Crystal color
Crystal habit
Crystal size (mm3)
a (Å)
b (Å)
c (Å)
Yellow
Plate
0.18 ꢃ 0.10 ꢃ 0.02
29.902(3)
10.9871(9)
7.6276(6)
O4–Si–C10
C10–Si–C11
C10–Si–C1
108.79(9)
111.35(12)
108.68(10)
O4–Si–C11
O4–Si–C1
C11–Si–C1
108.28(10)
108.22(8)
111.44(10)
a
b (°)
(°)
90
94.146(2)
90
2499.4(4)
c
(°)
V (Å3)
Crystal system
Space group
Z
Monoclinic
C2/c
8
1.532
1.01
Bruker SADABS program
100
0.71073
Graphite
Bruker SMART with Apex CCD
6967
2463 (0.0212)
Direct methods
hydrogen atom of the OH group of 7 is disordered over two posi-
tions with half occupancy at each site. The structure of 8 exhibits
the gauche orientation of arenechromiumtricarbonyl with respect
to the OH group, where as in 7 the orientation is anti. These two
features accounts for the H-bonding (HB) patterns noted in 7, vide
infra, which are largely absent in 8 presumably due to the steric
reasons.
Dcalc (g cmꢀ3)
l
(mmꢀ1
)
Absorption correction
T (K)
k (Å)
Monochromator
Diffractometer
Reflections collected
Independent reflections (Rint
Structure solution technique
Structure solution program
X-ray structures of
a number of organometallic silanols,
)
RR02SiOH (R = organometallic group), have been reported and the
majority of them exhibit some type of hydrogen-bonding dictated
by the steric demand of the organometallic group [13], Fig. 2. Thus,
discrete linear dimers [14,15], four-membered cyclic dimers,
[15,16] and tetrameric species are known [16,17] and we have re-
ported that the related ferrocenyl dimethylsilanol, FcSiMe2OH, 10
forms a cyclic H-bonded hexameric arrangement of SiOH groups
[18] reminiscent of hexameric forms of water [19]. The organome-
tallic silanols also form infinite chains depending upon the steric
demands of the substituents on silicon [17b].
SHELXS-97 (Sheldrick, 1990)
Full-matrix least-squares on F2
SHELXS-97 (Sheldrick, 1997)
Refinement technique
Refinement program
Function minimized
R
1.072
w(Fo2ꢀFc2)2
Goodness-of-fit (GOF) on F2
R1, wR2 [I>2r(I)]
0.0312, 0.0791
0.0332, 0.0806
R1, wR2 (all data)
0
The Si–C bond distances, in0the range of 1.847–1.878 ÅA, and a Si–O
bond distance of 1.652(1) ÅA are typical of organosilanols [11,13–
18]. The O–Si–C bond angles between 108.22–108.87° signify tet-
rahedral geometry and compare well with the reported values
for its diphenyl analog, {(g6 -C6H5)Cr(CO)3}Ph2SiOH, 8 [11]. The
In silanol 7, the hydrogen atom of the silanol group is0 disor-
dered over two positions, with O4ꢂꢂꢂO4B = 2.691 ÅA, O–
0
H41ꢂꢂꢂO4B = 159.6°, OꢂꢂꢂO4A = 2.708 ÅA and O–H42ꢂꢂꢂO4A = 154.3°).
The disorder is due to the centrosymmetric structure. This disorder
is also observed for {(g
5-C5Me5)(CO)2}FeCH2SiMe2OH (9) which

H.K. Sharma et al. / Journal of Organometallic Chemistry 695 (2010) 1168–1174
1171
SiPh2OH
SiMe2OH
Cr
Fe
CH2SiMe2OH
Fe
C
C
O
O
C
O
C
C
O
O
9
10
8
Fe
Fe
W
CH2SiMe2OH
Si
C
C
C
O
C
O
C
H
OH
O
O
C
O
PPh3
O
12
11
Fig. 2. Selected examples for orgamomatallic Silanols 8–12.
Fig. 3. Crystal packing of 7 exhibits H-bonding showing chain along the c axis illustrating head-to-head arrangement of the areneCr(CO)3 units.
crystallizes in the same spatial group C2/c generating the identical
HB motif (Fig. 3) [17b]. Both, compound 7 and 9, are amphiphiles
which are packed in head-to-head fashion with a HB chain running
parallel to the c axis of the crystal structure; where the hydropho-
bic Cr(CO)3 units are protecting the hydrophilic Si–OH groups
3. Experimental
3.1. General procedures
All syntheses were performed under an argon atmosphere using
standard Schlenk techniques. Tetrahydrofuran and hexanes were
distilled over sodium and benzophenone ketal. Hexamethylphosh-
oramide (HMPA) was distilled over calcium oxide. t-Butyllithium
(1.7 M in pentane), Me3SnCl and Cr(CO)6 were purchased from Al-
drich Chemicals; Me3SiCH2Cl and Me3GeCl were purchased from
Gelest; Me3PbBr was obtained from the bromination of Me4Pb
[21], PhMe2SiCH2GeMe3, 1 [7d], PhMe2Si(Me3Ge)(Me3Sn)CH, 2
(Fig. 4). The chain formed is not linear; it represents
a
spiro[2.2]pentane molecule as shown in (Fig. 5). The occurrence
of the chain instead of a 2-D bilayer is due to the generation of an-
other type of HB by the Cr(CO)3 units through the carbonyl groups
(C3–H3ꢂꢂꢂO1, 2.54 Å; C5–H5ꢂꢂꢂO2, 2.56 Å; C5–H5ꢂꢂꢂO3, 2.54 Å),
essentially identical interactions present in the crystal structure
of 9 [17b,20].

1172
H.K. Sharma et al. / Journal of Organometallic Chemistry 695 (2010) 1168–1174
room temperature and stirred overnight. The reaction was hydro-
lyzed with 25 mL of a 5% solution of NH4Cl at 0 °C. The organic
layer was extracted with 25 mL of hexanes and dried over MgSO4.
After filtration and removal of hexane on a rotary evaporator, the
liquid was distilled through a column at 110–114 °C at 0.05 mm
Hg to yield 3.1 g (40% yield) of 3.
3.2.1. Analytical and spectroscopic data for
(PhMe2Si)(GeMe3)(PbMe3)CH, 3
Anal. Calc. Found: C, 34.76 (35.05); H, 7.03 (6.93)%
1H: 0.076 (s, 9H, GeMe3); 0.25 (s, 3H, SiMe), 0.26 (s, 3H, SiMe);
0.25 (s, 1H, 2J207Pb–H = 90.6 Hz, CH); 0.63 (s, 9H, 2J207Pb–H = 57.0 Hz,
PbMe3); 7.25, 7.43(m, 5H, Ph).
13C: 1.01 (1JPb–C = 214.2 Hz, PbMe3); 1.16 (SiMe), 1.84 (3JPb–C
=
32.6 Hz, SiMe); 2.93 (3JPb–C = 25.4 Hz, GeMe3); 5.02 (CH), 127.66,
128.52, 133.40, 142.50 (ipso).
207Pb: 63.21.
29Si: ꢀ0.56 (2J29Si–207Pb = 37.5 Hz).
Fig. 4. View along the Si(OH) hydrogen-bonding chains illustrating the ribbon
character of the extended system, Si blue, O red.
3.3. Synthesis of {(g
6-C6H5)Cr(CO)3Me2Si}(Me3Ge)(Me3Pb)CH, 6
[5] were synthesized by the reported methods. NMR spectra were
recorded on a Bruker 300 MHz spectrometer using CDCl3 for 2 and
3 and using C6D6 for 4–7. IR spectra were recorded on a Perkin–El-
mer 1600 FT IR spectrophotometer. Elemental analyses were per-
formed by Galbraith Laboratories.
This synthesis is typical for all the new arenechromiumtricar-
bonyl complexes.
A
100 mL round-bottom flask was charged with 0.7 g
(1.35 mmol) of 3 and 0.3 g (1.36 mmol) of Cr(CO)6 in 20 mL of n-
butyl ether and 3 mL of THF. The mixture was heated in oil bath
under nitrogen atmosphere at 90 °C for 24 h. The color of the solu-
tion turned gray due to the deposition of lead. After 24 h, the tem-
perature of the oil bath was raised to 140 °C and mixture was
heated at this temperature for four days. The reaction mixture
was cooled to room temperature and filtered over Celite. Butyl
ether was removed by flash distillation under vacuum and the yel-
low residue was extracted with 10 mL of a 2:1 mixture of hexane
and toluene. Filtration and removal of the solvents produced yel-
low oil which solidified in the refrigerator to yield, 0.37 g (42%)
of 6, which was further recrystallized from a mixture of hexane
and toluene.
3.2. Synthesis of PhMe2Si(Me3Ge)(Me3Pb)CH, 3
A 250 mL Schlenk flask was charged with 20 mL of a THF solu-
tion containing 4.0 g (15 mmol) of PhMe2SiCH2GeMe3, 1, and 5 mL
of HMPA. The mixture was maintained at ꢀ78 °C and t-butyllith-
ium (15.0 mmol) was added dropwise via syringe. The solution be-
came yellow immediately and finally became orange and was
stirred for 90 min between ꢀ78 to ꢀ70 °C. At this time a THF slurry
of 4.98 g (15.0 mmol) of Me3PbBr was added slowly at the same
temperature. The color of the solution became bright yellow and
finally greenish-black. The solution was permitted to warm to
Fig. 5. View of the crystal packing through the c axis. Four chain motifs and the COꢂꢂꢂH hydrogen bonds are shown.

H.K. Sharma et al. / Journal of Organometallic Chemistry 695 (2010) 1168–1174
1173
3.3.1. Analytical and spectroscopic data for {(
(GeMe3)(PbMe3)CH, 6
g
6-C6H5)Cr(CO)3Me2Si}
3H SiMe), 0.31 (s, 3H, SiMe); 4.33 (t, J = 6 Hz, 2H, Ph), 4.70 (t, J = 6
Hz, 1H, Ph), 4.89 (d, J = 6 Hz, 2H, Ph).
Anal. Calc. Found: C, 33.04 (33.09); H, 4.62 (4.53)% m.p. 70–
13C: ꢀ5.48 (SnMe3); ꢀ1.74(CH); 0.88 (SiMe), 0.99 (SiMe);
3.02(GeMe3); 89.92, 95.61, 99.95 (Ph), 102.1 (ipso); 233.68 (CO).
119Sn: 12.51
72 °C.
1H: 0.043 (s, 1H, CH); 0.081 (s, 9 H, GeMe3); 0.29 (s, 3H SiMe),
2
0.31 (s, 3H, SiMe); 0.70 (s, 9H, J207Pb–H = 56.6 Hz, PbMe3); 4.36
29Si: 2.29 (2J29Si–119Sn = 24.3 Hz).
(t, J = 6 Hz, 2H, Ph), 4.72 (t, J = 6 Hz, 1H, Ph), 4.92 (d, J = 7.5 Hz, 2H, Ph).
13C: 0.88 (SiMe), 0.97 (SiMe); 1.50(1JPb–C = 218.0 Hz, PbMe3);
3.10 (GeMe3), 5.40 (CH); 90.00, 95.50, 99.80 (Ph), 102.6 (ipso);
233.67 (CO).
IR (m
CO) Hexane, cmꢀ1: 1977.5, 1911.7.
3.5. X-ray Crystal Structure for 7
207Pb: 59.36.
A yellow plate of silanol 7 was used for the X-ray crystallo-
graphic analysis. The X-ray intensity data were measured at
100(2) K on a Bruker SMART APEX CCD area detector system
29Si: 3.45 (2J29Si–207Pb = 44.5 Hz).
IR (
3.4. Synthesis of (
100 mL round-bottom flask was charged with 1.74 g
m
CO) Hexane, cmꢀ1: 1977.1, 1911.4.
equipped with a graphite monochromator and a Mo Ka fine-focus
g
6-C6H5)Cr(CO)3SiMe2OH, 7
sealed tube (k = 0.71073 Å). The structure was solved and refined
using the Bruker SHELXTL (Version 6.1) Software Package. A summary
of the relevant crystallographic parameters for 7 is presented
in Table 2, and selected bond lengths and angles are given in
Table 3.
A
(4.04 mmol) of 2 and 0.891 g (4.04 mmol) of Cr(CO)6 in 25 mL of
n-butyl ether and 5 mL of wet THF. The mixture was treated as
above for the synthesis of 6. After removal of butyl ether by flash
distillation under vacuum; a solid yellow residue (mixture of 4
and 7) was obtained. The mixture was treated with 15 mL 2:1 mix-
ture of hexanes and toluene, filtered and left in the refrigerator.
The silanol 7 was crystallized from the solution. Recrystallization
from toluene resulted in 0.29 g (25%) of 7. Evaporation of the sol-
vents from the filtrate produced crude 4 which was recrystallized
from hexane to yield 0.80 g (49%) of 4.
4. Conclusions
A convenient methodology for the synthesis of phenylsilyl
(germyl)stannyl-
and
phenylsilyl(germyl)plumbyl-methanes,
PhMe2Si(Me3Ge)(EMe3)CH, (E = Sn, Pb) and their arenechromium-
tricarbonyl-analogs is reported. The Sn–CH bond is labile in the
presence of water, and the Si–CH2 bond appears to be activated
by the areneCr(CO)3 substituent. The crystal structure of an arene-
chromiumtricarbonyl silanol exhibits intermolecular H-bonding
forming chains along the c axis with the head-to-head arrange-
ment of areneCr(CO)3 units which provide hydrophobic exterior
to hydrophilic silanol groups.
3.4.1. Analytical and spectroscopic data for (g
6-C6H5)Cr(CO)3SiMe2OH,
7
Anal. Calc. Found: C, 45.82 (45.59); H, 4.19 (4.22)%.
1H: 0.14 (s, 6H, SiMe2); 1.46 (1H, s, OH); 4.28 (t, J = 6 Hz, 2H, Ph),
4.62 (t, J = 6 Hz, 1H, Ph), 4.85 (d, J = 6 Hz, 2H, Ph).
13C: ꢀ0.40 (SiMe2); 90.34, 95.26, 97.97 (ipso) 98.85 (Ph); 233.46
(CO).
5. Supplementary material
29Si: 7.12.
CCDC 761242 contains the supplementary crystallographic data
for compound 7. The data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via <www.ccdc.cam.ac.uk/
data_request/cif>.
IR (m
CO) Hexane, cmꢀ1: 1978.0, 1911.7.
3.4.2. Analytical and spectroscopic data for {(g
6-C6H5)Cr(CO)3Me2Si}
(GeMe3)CH2, 4
Anal. Calc. Found: C, 44.70 (45.35); H, 5.50 (4.63)%, m.p. 79 °C
1H: ꢀ0.18 (s, 2H, CH2); 0.095 (s, 9H, GeMe3); 0.16 (s, 6H, SiMe2);
4.35 (t, J = 6 Hz, 2H, Ph), 4.80 (t, J = 6 Hz, 1H, Ph), 4.82 (d, J = 6 Hz,
2H, Ph).
Acknowledgments
This research has been supported by the NIH-MARC program
and the R. A. Welch Foundation, Houston, TX. (Grant # AH-0546).
The authors would like to thank Dr. Alejandro Metta for useful dis-
cussion with the crystal structure of the silanol 7.
13C: ꢀ0.63 (SiMe2); 0.72(GeMe3); 2.09 (CH2); 90.57, 95.02,
99.09 (Ph), 100.93 (ipso); 233.69 (CO).
29Si: 1.13.
IR (m
CO) Hexane, cmꢀ1: 1977.6, 1911.4.
References
3.4.3. Analytical and spectroscopic data for
(PhMe2Si)(GeMe3)(SnMe3)CH, 2
[1] (a) For the recent reviews on metalylenes and dimetallenes of group 14
elements, see: R. Okazaki, R. West, Adv. Organomet. Chem. 39 (1996) 231;
(b) T. Tsumuraya, S.A. Batcheller, S. Masumane, Angew. Chem., Int. Ed. 30
(1991) 902;
Anal. Calc. Found: C, 41.90 (42.2); H, 7.04 (6.93)%.
1H: ꢀ0.22 (s, 1H, 2J119Sn–H = 77.2 Hz, 2J117Sn–H = 74.0 Hz, CH); 0.05
(c) P.P. Power, Chem. Rev. 99 (1999) 3463;
(d) M. Weidenbruch, Coord. Chem. Rev. 130 (1994) 275;
(e) M. Kira, Pure Appl. Chem. 72 (2000) 2333;
(f) J. Barrau, J. Escudie, J. Satge, Chem. Rev. 90 (1990) 283;
(g) Z. Rappoport (Ed.), The Chemistry of Organic Germanium Tin and Lead
Compounds, vol 2, John Willey, 2002. Interscience;
(h) V.Y. Lee, A. Sekiguchi, Organometallics 23 (2004) 2822;
(i) H.K. Sharma, K.H. Pannell, in: R. Bruce King (Ed.), Encyl. Inorg. Chem, vol. 5,
John Willey & Sons, Chichester, 2005, pp. 2671–2680;
(j) K. Klinkhammer, Polyhedron 21 (2002) 587;
2
2
(s, 9H, J119Sn–H = 51.0 Hz, J117Sn–H = 49.8 Hz, SnMe3); 0.16 (s, 9H,
GeMe3); 0.33 (s, 3H, SiMe), 0.34 (s, 3H, SiMe); 7.32, 7.46 (m, 5H, Ph).
1
13C: ꢀ5.89 (1J119Sn–C = 328.0 Hz, J117Sn–C = 313.0 Hz, SnMe3);
ꢀ2.82 (1J 119Sn–C = 221.7 Hz, CH); 1.20 (SiMe), 1.53 (SiMe); 2.74
(GeMe3); 127.6, 128.5, 133.40, 142.0 (ipso).
119Sn: 14.1.
29Si: ꢀ1.72 (2J29Si–119Sn = 25.8 Hz).
(k) M. Widenbruch, Organometallics 22 (2003) 4348;
(l) M. Widenbruch, J. Organomet. Chem. 646 (2002) 39;
(m) Y. Wang, Y. Xie, P. Wei, R.B. King, H.F. Schaefer III, P. von R. Schleyer, G.H.
Robinson, Science 321 (2008) 1069.
3.4.4. Analytical and spectroscopic data for {(g
6-C6H5)Cr(CO)3Me2Si}
(GeMe3)(SnMe3)CH, 5
[2] (a) For disilynes, see: A. Sekiguchi, R. Kinjo, M. Ichinohe, Science 305 (2004)
1755;
Anal. Calc. Found: C, 38.21 (38.56); H, 5.34 (5.60), m.p 64 °C.
2
2
1H: ꢀ0.65 (s, 1H, J119Sn–H = 78 Hz, CH); 0.038 (s, 9H, J119Sn–H
=
(b) T. Sasamori, K. Hironaka, Y. Sugiyama, N. Takagi, S. Nagase, Y. Hosoi, Y.
Furukawa, N. Tokitoh, J. Am. Chem. Soc. 130 (2008) 13856;
51.6 Hz, 2J117Sn–H = 50.4 Hz, SnMe3); 0.087 (s, 9 H, GeMe3); 0.29 (s,

1174
H.K. Sharma et al. / Journal of Organometallic Chemistry 695 (2010) 1168–1174
(c) For distannenes, see: P.J. Davidson, M.F. Lappert, J. Chem. Soc., Chem.
Commun. (1973) 317;
[11] K.L. Malisza, L.C.F. Chao, J.F. Britten, B.G. Sayer, G. Jaouen, S. Top, A. Decken, M.J.
McGlinchey, Organometallics 12 (1993) 2462.
(d) V. Ya Lee, T. Fukawa, M. Nakamoto, A. Sekiguchi, B.L. Tumanskii, M. Karni,
Y. Apeloig, J. Am. Chem. Soc. 128 (2006) 11643.
[12] M. Morán, I. Cuadrado, M.C. Pascual, C.M. Casado, Organometallics 11 (1992)
1210.
[3] (a) K. Itami, M. Mineno, T. Kamei, J. Yoshida, Org. Lett. 4 (2002) 3635;
(b) M. Shimizu, T. Hata, T. Hiyama, Tetrahedron Lett. 40 (1999) 7375.
[4] K.K. Wang, S. Dhumrongvaraporn, Tetrahedron Lett. 28 (1987) 1007.
[5] F. Cervantes-Lee, H.K. Sharma, A.M. Haiduc, K.H. Pannell, J. Organomet. Chem.
686 (2003) 379.
[13] V. Chandrasekhar, R. Boomishankar, S. Nagendran, Chem. Rev. 104 (2004)
5847.
[14] M.J. MacLachlan, J. Zheng, K. Thieme, A.1. Lough, I. Manners, C. Mordas, R.
LeSuer, W.E. Geiger, L.M. Liable-Sands, A.L. Rheingold, Polyhedron 19 (2000)
275.
[6] M. Shimizu, T. Kurahashi, H. Kitagawa, K. Shimono, T. Hiyama, J. Organomet.
Chem. 686 (2003) 286.
[15] S. Moller, O. Fey, W. Malisch, W. Seelback, J. Organomet. Chem. 507 (1996)
239.
[7] (a) A.R. Bassindale, A.J. Bowles, M.A. Cook, C. Eaborn, A. Hudson, R.A. Jackson,
A.E. Jukes, J. Organomet. Chem. 24 (1970) 529;
[16] W. Malisch, M. Vögler, D. Schumacher, M. Nieger, Organometallics 21 (2002)
2891.
(b) F. Glockling, N.M.N. Gowda, Inorg. Chim. Acta 58 (1982) 49;
(c) B. Wrackmeyer, H. Zhou, Spectrochim. Acta, Part A 47A (1991) 849;
(d) S. Inoue, Y. Sato, Organometallics 8 (1989) 1237;
(e) T.N. Mitchell, A. Amamria, B. Fabisch, J. Organomet. Chem. 259 (1983)
157.
[17] (a) W. Malisch, M. Hofmann, G. Kaupp, H. Käb, J. Reising, Eur. J. Inorg. Chem.
(2002) 3235;
(b) W. Malisch, M. Hofmann, M. Nieger, W. Schöller, A. Sundermann, Eur. J.
Inorg. Chem. (2002) 3242.
[18] H.K. Sharma, F. Cervantes-lee, I. Haiduc, K.H. Pannell, Appl. Organomet. Chem.
19 (2005) 437.
[19] R. Ludwig, Angew. Chem., Int. Ed. 40 (2001) 1808.
[20] CSD, version 5.29 Cambridge Crystallographic Data Centre: UK, Sep 2009.
[21] H. Gilman, R.G. Jones, J. Am. Chem. Soc. 72 (1950) 1760.
[8] S.B. Nagelberg, C.E. Reinhold, B.R. Willeford, M.P. Bigwood, K.C. Molloy, J.J.
Zuckerman, Organometallics 1 (1982) 851.
[9] K. H. Pannell, F. Ratel, Manuscript in preparation.
[10] D.W. Hawker, P.R. Wells, Organometallics 4 (1985) 821.