Lithiated γ-O-functionalized propyl phenyl sulfides and sulfones of the type Li[CH(SOxPh)CH2CH2OR] (x = 0, 2). [Li{CH(SPh)CH2CH2Ot-Bu}(tmeda)] - A structurally characterized organolithium inner comple

Article abstract of DOI:10.1016/j.jorganchem.2009.05.035

Lithiation of O-functionalized alkyl phenyl sulfides PhSCH₂CH₂CH₂OR (R = Me, 1a; i-Pr, 1b; t-Bu, 1c; CPh₃, 1d) with n-BuLi/tmeda in n-pentane resulted in the formation of α- and ortho-lithiated compounds [Li{CH(

Full text of DOI:10.1016/j.jorganchem.2009.05.035

Journal of Organometallic Chemistry 694 (2009) 3353–3361
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Lithiated
c-O-functionalized propyl phenyl sulfides and sulfones of the type
Li[CH(SOxPh)CH2CH2OR] (x = 0, 2). [Li{CH(SPh)CH2CH2Ot-Bu}(tmeda)] – A
structurally characterized organolithium inner complex
Michael Block a, Matthias Linnert a, Santiago Gómez-Ruiz b, Dirk Steinborn a,
*
a Institut für Chemie, Martin-Luther-Universität Halle-Wittenberg, Kurt-Mothes-Straße 2, D-06120 Halle, Germany
b Departamento de Química Inorgánica y Analítica, E.S.C.E.T., Universidad Rey Juan Carlos, 28933 Móstoles, Madrid, Spain
a r t i c l e i n f o
a b s t r a c t
Article history:
Lithiation of O-functionalized alkyl phenyl sulfides PhSCH2CH2CH2OR (R = Me, 1a; i-Pr, 1b; t-Bu, 1c; CPh3,
Received 24 November 2008
Received in revised form 22 April 2009
Accepted 27 May 2009
1d) with n-BuLi/tmeda in n-pentane resulted in the formation of
[Li{CH(SPh)CH2CH2OR}(tmeda)] ( -2a–d) and [Li{o-C6H4SCH2CH2CH2OR)(tmeda)] (o-2a–d), respectively,
which has been proved by subsequent reaction with n-Bu3SnCl yielding the requisite stannylated -OR-
functionalized propyl phenyl sulfides n-Bu3SnCH(SPh)CH2CH2OR -3a–d) and n-Bu3Sn(o-
C6H4SCH2CH2CH2OR) (o-3a–d). The /ortho ratios were found to be dependent on the sterical demand
of the substituent R. Stannylated alkyl phenyl sulfides -3a–c were found to react with n-BuLi/tmeda
and n-BuLi yielding the pure -lithiated compounds -2a–c and [Li{CH(SPh)CH2CH2OR}] ( -4a–b),
respectively, as white to yellowish powders. Single-crystal X-ray diffraction analysis of [Li{CH(SPh)CH2-
CH2Ot-Bu}(tmeda)] ( -2c) exhibited a distorted tetrahedral coordination of lithium having a chelating
tmeda ligand and a C,O coordinated organyl ligand. Thus, -2c is a typical organolithium inner complex.
Lithiation of O-functionalized alkyl phenyl sulfones PhSO2CH2CH2CH2OR (R = Me, 5a; i-Pr, 5b; CPh3, 5c)
with n-BuLi resulted in the exclusive formation of the -lithiated products Li[CH(SO2Ph)CH2CH2OR] (6a–
c) that were found to react with n-Bu3SnCl yielding the requisite -stannylated compounds n-Bu3SnCH(-
a- and ortho-lithiated compounds
a
c
Available online 3 June 2009
(
a
a
Dedicated to Professor Ingo-Peter Lorenz on
the occasion of his 65th Birthday.
a
a
a
a
Keywords:
a
O-functionalized sulfides
O-functionalized sulfones
Regioselective lithiations
Tin–lithium transmetallation
Organolithium inner complexes
a
a
a
SO2Ph)CH2CH2OR (7a–c). The identities of all lithium and tin compounds have been unambiguously
proved by NMR spectroscopy (1H, 13C, 119Sn).
Ó 2009 Elsevier B.V. All rights reserved.
1. Introduction
temperature a carbenoid reactivity [8]. Thus, the degree of aggrega-
tion seems to be decisive for the reactivity. In the case of the sulfo-
Since the reports of Köbrich on the carbenoid properties of halo-
genmethyl lithium compounds (‘‘Köbrich’s carbenoids”) [1], hetero-
atom-functionalized methyllithium compounds have been in the
focus of many investigations [2,3]. Compounds of the types Li-
CH2YRn (I) and LiCH2YOxRn (II) having Lewis-basic (YRn = OR, SR,
NR2, PR2, etc.; R = alkyl, aryl) and dipole stabilized [4] (YOxRn = POR2;
SOR, SO2R, etc; R = alkyl, aryl) functionalizations, respectively, are of
special interest. In the case of Köbrich’s thermally highly unstable
compounds, an intramolecular interaction between the halo sub-
stituents and lithium atoms play a crucial role for the carbenoid
properties [5]. On the other hand, also intermolecular interactions
between the Lewis-basic heteroatom with the lithium center may
have a severe influence on the stability and reactivity of these com-
pounds. Thus, in contrast to the dinuclear S-functionalized com-
pounds [{LiCHR0SR}2] (Ia; R = alkyl, aryl; R0 = H, alkyl, aryl) [6,7]
only the monomeric derivative [Li(CH2SPh)(pmdta)] (pmdta = N,
N,N0,N00,N00-pentamethyldiethylenetriamine) exhibited at elevated
nylmethyl lithium compounds [Li(CH2SO2R)Lx] (IIa, L = neutral N
or O donor) the manner of the Li coordination ( -C vs. O) was found
a
to be essential for their structures and reactivities [9–11].
Lithiation reactions of alkyl phenyl sulfides resulting in type Ia
compounds (R0 = alkyl, R = Ph) were found to proceed with differ-
ent regioselectivities (a
- vs. ortho-lithiation) depending on R0
[12]. The introduction of a donor function in R0 in a position favor-
ably for intramolecular coordination may give rise to the formation
of organometallic inner complex formation. Thus,
alized propyl phenyl sulfides PhSCH2CH2CH2NR2 were found to fa-
vor the -lithiation yielding such inner complexes [13,14]. Here,
we report on the regioselectivities in lithiation reactions of -OR-
c-NR2-function-
a
c
functionalized propyl phenyl sulfides PhSCH2CH2CH2OR (1aꢀd)
and on tin–lithium transmetallation reactions yielding sulfur-func-
tionalized organolithium compounds of the type LiCH(SPh)CH2
CH2OR. Structural investigations gave proof that the tert-butoxy
derivative (R = t-Bu,
a-1a) is an organometallic inner complex in
the solid state. Furthermore, we report on lithiation reactions of
the requisite sulfone derivatives resulting in lithium compounds
of the type Li[CH(SO2Ph)CH2CH2OR] (6aꢀc).
* Corresponding author. Tel.: +49 345 55 25620; fax: +49 345 55 27028.
E-mail address: dirk.steinborn@chemie.uni-halle.de (D. Steinborn).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.05.035

3354
M. Block et al. / Journal of Organometallic Chemistry 694 (2009) 3353–3361
Table 1
2. Results and discussion
2.1. Lithiation of PhSCH2CH2CH2OR
Degree of conversion (in %) and a/ortho ratios (given in parentheses) for the lithiation
and subsequent stannylation of O-functionalized sulfides (1a–d) according to Scheme
1. For comparison (taken from Ref. [14]) the requisite values for the menthyl (Men)
and borneyl (Bor) derivatives are also given.
The c-OR-functionalized propyl phenyl sulfides, PhS-CH2-CH2-
R
t = 1a
t = 24a
t = 72a
CH2OR (R = Me, 1a; i-Pr, 1b; t-Bu, 1c; CPh3, 1d) have been obtained
by conventional methods from PhSCH2CH2CH2Br and PhSCH2
CH2CH2OH, respectively (see Section 3). Compounds 1a–d were
3a
3b
3c
3d
Me
72 (95:5)
65 (65:35)
76 (52:48)
92 (100:0)
91 (81:19)
86 (66:34)
85 (58:42)
90 (73:27)
90 (68:32)
94 (100:0)
93 (92:8)
91 (79:21)
i-Pr
t-Bu
CPh3
Men
Bor
found to react with n-BuLi/tmeda in n-pentane yielding the
a-
and ortho-lithiated compounds 2a–d as revealed by the subse-
quent reaction with n-Bu3SnCl yielding the requisite stannylated
-OR-functionalized propyl phenyl sulfides 3a–d (Scheme 1).
a
c
t is the reaction time in h.
Both, lithiation and stannylation proceeded at room tempera-
ture with a high degree of conversion (>85%). The
were found to be time dependent showing that the ortho deriva-
tives are the kinetically controlled products whereas the deriva-
tives are under thermodynamic control (Table 1), as it has already
been shown in lithiation reactions of PhSMe [15]. In accordance
with that 13C NMR spectroscopic investigations of the reaction
mixture 1c/n-BuLi/tmeda in deuterated benzene revealed after
about 15 min a high portion of the ortho-lithiated product o-3c
which was decreased in the course of reaction with concomitant
a/ortho ratios
the magnitude of the 1J(119Sn,13CBu) coupling constant the lower
the electronic influence of R0 [16,17]. Inspection of Table 2 reveals
that the electronic influence of the groups R0 = CH(SPh)CH2CH2OR
a
is not significantly dependent on the substituent R (
a-3a–c:
325.6–328.7 Hz). Furthermore, the electronic influence proved to
be roughly the same as that of other
a-S-functionalized groups
such as R0 = CH2SPh (321.2 Hz [18]) and R0 = CH(Me)SPh (323.0 Hz
[12]) but smaller than that of R0 = CMe(Ph)SPh (310.9 Hz [14]).
All these values are in-between those of the methyl (R0 = Me,
330.1 Hz [17]) and the ethyl group (R0 = Et, 319.0 Hz [19]).
increase of the portion of the
results could be obtained in the lithiation reaction of 1b.
The quantitative evaluation of the /ortho ratios of the air-sta-
ble stannylated compounds -3/o-3 revealed a strong dependency
on the sterical demand of the -OR substituent, see Table 1 (col-
a-lithiated product a-3c. Analogous
a
a
2.2. Tin–lithium transmetallion of n-Bu3SnCH(SPh)CH2CH2OR
c
umn 4): With the increasing bulkiness of the ‘‘parent” primary
(Me), secondary (i-Pr) and tertiary (t-Bu) alkyl groups R, the por-
The
smoothly in hydrocarbons (n-pentane) with n-BuLi/tmeda in a
tin–lithium transmetallation reaction yielding the pure -lithiated
sulfides -2a–c (Scheme 2). The organolithium compounds -2a–c
could be isolated as colorless to yellowish powders in (isolated)
yields between 51% and 89%. In contrast to this, metallation of
the sulfides 1b/c with n-BuLi/tmeda according to Scheme 1 gave
a-stannylated sulfides a-3a–c were found to react
tion of the
with that the sterically highly demanding CPh3 derivative gave
42% ortho product. The /ortho ratios (values taken from Ref.
a-product decreases from 100% to 66%. In accordance
a
a
a
a
[14]) for the secondary and sterically highly demanding menthyl
(Men) and borneyl (Bor) derivatives lie – as expected – between
the sterically less demanding secondary isopropoxy (3b) and the
tertiary tert-butoxy (3c) derivatives.
only mixtures of
a- and ortho-lithiated products; experiments to
isolate these lithium compounds resulted in the formation of oily
Fractional distillation under vacuum of the stannylated sulfides
products only. Although the requisite lithiation reaction starting
3a–c (
ucts -3a–c that were obtained as colorless to pale yellow oils in
(isolated) yields between 49% and 81%, whereas the distillation
a/ortho mixtures) resulted in the pure a-stannylated prod-
from 1a led to the exclusive formation of the
lithium transmetallation reaction proved to be superior because
a pure solid compound could be isolated.
a-product, the tin–
a
of
a-3d failed due to its high boiling point. The identities of a-
The lithiated compounds a-2a–c were not only highly moisture
3a–c have been confirmed by microanalysis, 1H, 13C and 119Sn
NMR spectroscopy (Table 2). In tetraorgano tin compounds of the
type n-Bu3Sn–R0 the 1J(119Sn,13CBu) coupling constants reflect the
electronic influence of the substituents R0 such that the higher
sensitive but even pyrophoric. They were well soluble in THF.
These solutions were found to be stable at ꢀ40 °C whereas at room
temperature decomposition was observed within 1 day. Further-
more, there was found an increasing solubility (R = Me < i-Pr < t-
N
N
N
N
Li
Li
n
n
-BuLi/tmeda
-pentane
S
CH2CH2CH2 OR
S
CHCH2CH2 OR
S
CH2CH2CH2 OR
1a−d
2a−d
n
-pentane
n
-Bu3SnCl
n
Sn( -Bu)3
n
Sn( -Bu)3
S
CH2CH2CH2 OR
S
CHCH2CH2 OR
3a−d
a
b
c
d
R
Me
i
-Pr
t
-Bu CPh3
Scheme 1. Synthesis of lithiated (2a–d) and stannylated c-OR functionalized sulfides (3a–d).

M. Block et al. / Journal of Organometallic Chemistry 694 (2009) 3353–3361
3355
Table 2
ꢀ10 °C. The compound crystallized in isolated monomeric mole-
cules without unusual intermolecular interactions (shortest dis-
tance between non-hydrogen atoms: 3.492(7) Å, C2ꢁ ꢁ ꢁC160). The
molecular structure is shown in Fig. 1, selected geometrical param-
eters are given in Table 3. The primary donor set of Li is built up by
Selected NMR spectroscopic data (d in ppm, J in Hz) of
Bu3SnCH(SPh)CH2CH2OR (
a-stannylated sulfides n-
a
-3aꢀc).
(1JSn,C
R
d
)
d
(1JSn,C
a-C (Bu)
)
d(119Sn)
a
-C
a-3a
a-3b
a-3c
Me
i-Pr
t-Bu
25.1 (250.8)
24.9 (249.2)
24.9 (247.5)
10.2 (328.7)
10.0 (325.9)
10.0 (325.6)
ꢀ10.7
ꢀ9.7
ꢀ9.5
two N atoms of the tmeda ligand as well as by the
a-C and the O
atom of the organo ligand. Thus, -2c is a typical organolithium in-
a
ner complex having a distorted tetrahedral coordination of Li. The
chelate bindings of the tmeda and the organo ligand give rise to
relatively small angles N1–Li–N2 (87.2(3)°) and C7–Li–O
(88.0(3)°) with concomitant enlargement of the angles N2–Li–O
(131.6(4)°) and N2–Li–C7 (122.3(4)°). Both of the five-membered
rings (C2N2Li) and (C3LiO) exhibit an envelope conformation
twisted on C17 and C9, respectively. The LiꢀC7 bond length
(2.151(9) Å) is in the expected range [21]. The Li–O bond
(1.984(7) Å) was also found to be in the expected range as the com-
parison with Li–O bonds in other complexes of tetrahedral coordi-
nated lithium showed (median: 1.968 Å, lower/higher quartile:
1.938/2.004 Å; n = 131, n – number of observations [21]). The Liꢁ ꢁ ꢁS
distance of 3.337(1) Å indicates that there are no interactions be-
tween these two atoms.
Bu) in benzene and these solutions were stable for a longer period
even at room temperature. When the tin–lithium transmetalla-
tions were performed in absence of tmeda (
a-3a/b + n-BuLi), the
lithiated products -4a/b were also found to be solids. In contrast
a
to the tmeda adducts, they were only soluble in coordinating sol-
vents such as THF whereas these solutions were also not stable
at room temperature. All these findings indicate that the tmeda-
free products are of higher aggregation in the solid state. In
contrast to that – at least the tmeda adduct
monomeric in the solid state (vide infra).
a-2c – proved to be
The identities of the lithiated compounds
firmed by 1H and 13C NMR spectroscopy and in the case of tert-but-
oxy derivative ( -2c) also by single-crystal X-ray diffraction
analysis. In that case also the inspection of the 1J( 13C,1H) cou-
pling constant revealed a decrease upon lithiation by 10 Hz
(130 Hz in -2c vs. 140 Hz in 1c) being in accordance with an
a
-2a–c were con-
a
a
-
2.4. Lithiation of PhSO2CH2CH2CH2OR
a
a-
The c-OR-functionalized propyl phenyl sulfones, PhSO2CH2CH2-
C–Li bond also in THF solution as expected [20]. Due to the high
CH2OR (R = Me, 5a; i-Pr, 5b), have been obtained by oxidation of
the respective sulfides PhSCH2CH2CH2OR 1a, b with acetic acid/
hydrogen peroxide whereas 5c (R = CPh3) was received by reaction
of PhSO2CH2CH2CH2OH with Ph3CCl in presence of DBU (see Sec-
tion 3). Compounds 5a–c were found to react with n-BuLi in n-pen-
tane (5a/b) or in toluene (5c) at room temperature yielding the
quadrupole moment of the most abundant lithium isotope 7Li
(I = 3/2, 92.6% abundance) the signals of the b- and
the alkyl chains in -2a–c appeared broad whereas, surprisingly,
the -proton signals remained to be sharp. The -protons were
c-protons of
a
a
a
found strongly highfield shifted (0.88ꢀ0.92 ppm) compared to
the sulfides 1aꢀc (2.99ꢀ3.00 ppm). The signals of all other protons
also remained to be sharp and showed smaller shifts (up to
0.4 ppm) upon lithiation. In the 13C NMR spectra the signals for
a
-lithiated compounds 6a–c (Scheme 4). In contrast to the sulfides
(1a–c) only -lithiation and no ortho-metallation was observed
which is due to the higher acidity of the -protons in sulfones.
a
a
the
a
-C atoms (15.5ꢀ15.8 ppm in
a
-2a–c vs. 30.4ꢀ30.5 ppm in
For this reason, the metallation could also be performed with n-
BuLi in absence of an N-donor co-ligand.
The lithiated sulfones 6a–c were isolated in high yields as white
to pale yellow powders. They proved to be moisture and air sensi-
1aꢀc) and for the i-C atoms of the phenyl substituents
(152.1ꢀ152.4 ppm in
a-2a–c vs. 136.6ꢀ136.8 ppm in 1aꢀc)
showed the most significant shifts.
Furthermore, the synthesis of lithiated sulfides via tin–lithium
transmetallation opened up an alternative way to proof that ortho-
and a-lithiation of the sulfides (see Table 1) are under kinetic and
thermodynamic control, respectively. Thus, an ortho-stannylated
enriched mixture of the methoxy functionalized derivatives o-3a
tive but less reactive than the analogous lithiated sulfides a-2a–c.
All lithiated sulfones were unsoluble in non-coordinating solvents
like n-pentane or toluene. They showed a decreasing solubility in
THF and DMSO (R = Me > i-Pr > CPh3). While the THF solutions
could be handled at room temperature without decomposition,
in the case of the DMSO solutions a color change from yellow to
black within few hours gave proof of a decomposition at room tem-
perature. The identities of the lithiated compounds 6a–c have been
confirmed by 1H and 13C NMR spectroscopy. In the case of the
methoxy functionalized lithiated sulfone 6a an increase of the
and a-3a (80:20) was prepared by metallation of 1a quenched with
n-Bu3SnCl after 30 min and subsequent chromatographic work-up
(Scheme 3). The following transmetallation with n-BuLi/tmeda and
the repeated reaction with n-Bu3SnCl after 12 h led to the exclusive
formation of the
a-stannylated product a-3a.
a-
1J( 13C,1H) coupling constant by 10 Hz (147 Hz in 6a vs. 137 Hz
2.3. Molecular structure of [Li{CH(SPh)CH2CH2Ot-Bu}(tmeda)]
in 5a) indicates that the lithium atom is not coordinated to the
a
-C atom [20a,22] but to the O atoms of the sulfonyl group as usu-
ally found in lithiated sulfones [9,23–25]. A comparison of the 1H
Crystals of [Li{CH(SPh)CH2CH2Ot-Bu}(tmeda)] (
a-2c) suitable
for X-ray diffraction analysis were obtained from n-pentane at
NMR spectra of the lithiated sulfones 6aꢀc to the requisite
N
Li
CH O R
N
Sn(n-Bu)3
n
-BuLi/tmeda
-pentane
S
S
CHCH2CH2 OR
n-Bu4Sn
n
H2C CH2
α-3a−c
α-2a−c
a
b
c
R
Me
i-Pr t-Bu
Scheme 2. Synthesis of a-lithiated c-OR functionalized sulfides (a-2a–c) by tin–lithium transmetallation.

3356
M. Block et al. / Journal of Organometallic Chemistry 694 (2009) 3353–3361
Sn(
n
-Bu)3
CH2CH2CH2 OMe
o
-3a (80 %)
1)
n
-BuLi/tmeda
(0.5 h)
n
Sn( -Bu)3
S
CH2CH2CH2 OMe
S
CHCH2CH2 OMe
S
2)
n
-Bu3SnCl
1a
3) chromatographic
work-up
α-3a (20 %)
1)
2)
n
-BuLi/tmeda (12 h)
n
-Bu3SnCl
Sn(
n
-Bu)3
S
CHCH2CH2 OMe
α-3a (100 %)
Scheme 3. To the ortho/
a
isomerization of the lithiated
c
-OMe functionalized sulfide o-3a.
sulfones 5aꢀc revealed that the most significant highfield shifts
were found for the
C13
C10
a
-protons (1.70ꢀ1.75 ppm in 6aꢀc vs.
C12
3.12ꢀ3.22 ppm in 5aꢀc) while all other signals showed smaller
differences. In the 13C NMR spectra the most distinct shifts were
C9
observed for the signals of the
a
-C (42.2ꢀ45.2 ppm in 6aꢀc vs.
O
53.6ꢀ53.9 ppm in 5aꢀc) and i-C atoms (152.4ꢀ155.8 ppm in
C11
C8
6aꢀc vs. 139.1ꢀ139.2 ppm in 5aꢀc).
The synthesis of the c-OR-functionalized stannylated sulfones
C14
Li
C18
C15
C17
7aꢀc was done by lithiation of the sulfones 5aꢀc as described
C7
C5
C6
N1
above followed by addition of n-Bu3SnCl (Scheme 4). Chromato-
C4
S
graphic work-up of the reactions mixtures gave the pure a-stanny-
lated products 7a–c as colorless to pale yellow oils with (isolated)
yields of 42ꢀ62%. Their identities have been confirmed by micro-
analysis and 1H, 13C and 119Sn NMR spectroscopy (Table 4). The
1J(119Sn,13CBu) coupling constants (337.0–338.9 Hz) were found to
be in a very narrow range being in accordance with the requisite
couplings in other n-Bu3SnCH(SO2Ph)CH2CH2OR derivatives
(R = Men, 336.4 Hz [26]; Bor, 336.9 Hz [14]). As comparison to
the structurally similar – but non-OR-functionalized – ligand
CH(Me)SO2Ph (329.2 Hz [27]) and CH(Bn)SO2Ph (336.9 Hz [27]) re-
N2
C1
C3
C2
C16
C19
Fig. 1. Molecular structure of [Li{CH(SPh)CH2CH2Ot-Bu}(tmeda)] in crystals of
2c. The ellipsoides are shown with a probability of 50%. H atoms have been omitted
a-
for clarity.
vealed, the
tronic influence. On the other hand, the substitution pattern of the
-C atom influences the electronic properties of -sulfonyl ligands:
the 1J(119Sn,13CBu) coupling constants of the compounds having
secondary -C atoms (329.2–338.9 Hz) lie in-between of those
having tertiary (n-Bu3SnCMe(Et)SO2Ph, 325.6 Hz [25]) and primary
(n-Bu3SnCH2SO2Ph, 346.1 Hz [28]) -C atoms, respectively.
c-OR substituent does not significantly affect the elec-
Table 3
Selected bond lengths (in Å) and angles (in °) of [Li{CH(SPh)CH2CH2Ot-Bu}(tmeda)]
(a-2c).
a
a
Li–C7
Li–O
Li–N1
Li–N2
C7–S
C7–C8
C8–C9
C9–O
2.151 (9)
1.984 (7)
2.191 (8)
2.111 (9)
1.737 (5)
1.548 (6)
1.465 (7)
1.430 (6)
C7–Li–C8
N1–Li–N2
N1–Li–O
N2–Li–O
O–Li–C9
O–Li–C7
N1–Li–C7
N2–Li–C7
99.5 (4)
87.2 (3)
118.6 (4)
131.6 (4)
105.9 (3)
88.0 (3)
a
a
In summary, the investigations gave proof that in lithiation
reactions of alkyl phenyl sulfides bearing a Lewis-basic substituent
110.6 (4)
122.3 (4)
in chelating favored position (c-OR group) the regioselectivity
(a/ortho ratio) can be understood in terms of an inner complex
O
n
-BuLi
Li PhSCHCH2CH2OR
n
-pentane
O
6a−c
a
b
ca)
-Pr CPh3
O
S
R
Me
i
Ph
CH2CH2CH2 OR
yield 6 in % 81 79
yield 7 in % 62 50
78
42
O
5a−c
a) in toluene
1.
2.
n
-BuLi
O
S
Sn(n-Bu)3
n-Bu3SnCl
Ph
CHCH2CH2 OR
n-pentane
O
7a−c
Scheme 4. Lithiation and stannylation of O-functionalized sulfones.

M. Block et al. / Journal of Organometallic Chemistry 694 (2009) 3353–3361
3357
Table 4
temperature the mixture was neutralized with aqueous ammonia
and diluted with water (150 ml). The aqueous phase was extracted
with diethyl ether (3 ꢂ 80 ml) and the combined organic extracts
were dried (Na2SO4). After evaporation of the solvents the residue
was purified by means of column chromatography (silica; n-pen-
tane/diethyl ether 3:1). Yield: 14.0 g (63%). Bp: 73–75 °C (0.06 Torr).
1H NMR (400 MHz, CDCl3): d 1.17 (s, 9H, OC(CH3)3), 1.84 (m, 2H,
CH2CH2CH2), 2.99 (m, 2H, CH2SPh), 3.43 (m, 2H, CH2OCCH3), 7.11–
7.16 (m, 1H, p-H, SPh), 7.22–7.27 (m, 2H, m-H, SPh), 7.30–7.33 (m,
2H, o-H, SPh). 13C NMR (100 MHz, CDCl3): d 27.6 (s, OC(CH3)3), 30.2
(s, CH2CH2CH2), 30.5 (s, 1J(13C,1H) = 140 Hz, CH2SPh), 59.8 (s,
OC(CH3)3), 72.7 (s, CH2OCCH3), 125.2 (s, p-C, SPh), 128.4 (s, m-C,
SPh), 129.5 (s, o-C, SPh), 136.8 (s, i-C, SPh). (Here and in the following
CAH coupling constants were obtained from H-coupled 13C NMR
spectra.)
Selected NMR spectroscopic data (d in ppm, J in Hz) of stannylated sulfones 7aꢀc.
d
(1JSn,C
)
d
(1JSn,C
)
d (119Sn)
a
-C
a-C (Bu)
7a
7b
7c
Me
i-Pr
CPh3
50.9 (129.3)
50.9 (134.5)
51.0 (126.4)
11.9 (338.9)
11.7 (337.6)
11.5 (337.0)
2.6
3.7
2.7
formation that depends on the sterical demand and the electronic
properties of the alkoxy substitution. This inner complex formation
gives rise to a stabilization of the
ortho-lithiated ones. Thus, the formation of a proper substrate–
alkyllithium complex en route to lithiation seems to be decisive
a-lithiated derivatives over the
both for ortho- and
substituted hydrocarbons [29]. In the requisite sulfones exclusively
a-lithiation as known for other heteroatom
a
a
-lithiated products were obtained due to the higher acidity of the
-protons.
R = CPh3 (1d). To a stirred solution of PhSCH2CH2CH2OH (12.6 g,
0.08 mol) and chlorotriphenylmethane (25.1 g, 0.09 mol) in dichlo-
romethane (150 ml), 1,8-diazabicyclo[5.4.0]undec-7-ene (5.3 g,
0.04 mol) was added dropwise. After stirring for 2 days the solu-
tion was diluted with water (300 ml). The aqueous phase was ex-
tracted with dichloromethane (3 ꢂ 150 ml) and the combined
organic extracts were dried (Na2SO4). After filtration and evapora-
tion of the solvent under reduced pressure the residue was purified
by means of column chromatography (silica; n-pentane/diethyl
ether 1:1). Yield: 7.6 g (30%).
3. Experimental section
3.1. General comments
Organolithium compounds were prepared and handled under
purified argon using standard Schlenk techniques. n-Pentane,
n-hexane, diethyl ether, THF, benzene, toluene, toluene-d8, ben-
zene-d6 and THF-d8 were distilled from sodium benzophenone
ketyl. DMSO-d6 was dried over molecular sieve 4A. NMR spectra
were recorded on Varian Gemini 200, Gemini 2000, and Varian
500 spectrometers using the protio impurities and the 13C reso-
nances of the deuterated solvents as references for 1H and 13C
NMR spectroscopy, respectively. d(119Sn) is relative to external
SnMe4 in C6D6. The preparative centrifugally accelerated thin layer
chromatography was made by using a Chromatotron (Harrison
Research). Reactions of BrCH2CH2CH2X (X = OH, Br) with KSPh in
MeOH afforded PhSCH2CH2CH2X.
1H NMR (400 MHz, CDCl3): d 1.88ꢀ1.94 (m, 2H, CH2CH2CH2),
3.02 (m, 2H, CH2SPh), 3.18 (m, 2H, CH2OCPh3), 7.12–7.42 (m,
12H, p-H, SPh + p-H, OCPh3 + m-H, SPh + m-H, OCPh3 + m, 8H, o-H,
SPh + o-H, OCPh3). 13C NMR (100 MHz, CDCl3):
d 30.0 s, (s,
CH2CH2CH2), 30.7 (s, CH2SPh), 62.2 (s, CH2OCPh3), 86.6 (s, Ph3CO),
125.7 (s, p-C, SPh), 126.9 (s, p-C, Ph3CO), 127.7 (s, m-C, SPh),
128.7 (s, o-C, SPh), 128.8 (s, m-C, Ph3CO), 129.1 (s, o-C, Ph3CO),
136.6 (s, i-C, SPh), 144.2 (s, i-C, Ph3CO).
3.3. Preparation of n-Bu3SnCH(SPh)CH2CH2OR (R = Me,
3b; t-Bu, -3c; CPh3, -3d)
a-3a; i-Pr, a-
a
a
3.2. Preparation of PhSCH2CH2CH2OR (1a–d)
At ꢀ78 °C to a stirred solution of n-BuLi (0.01 mol, 1.5 M in n-
hexane) and tmeda (1.16 g, 0.01 mol) in n-pentane (20 ml) the
respective compound 1a–d (0.01 mol) was added slowly via a syr-
inge. After stirring for 24 h at room temperature n-Bu3SnCl (3.2 g,
0.01 mol) was added dropwise. To the suspension obtained a satu-
rated aqueous solution of NH4Cl (15 ml) was added. The aqueous
phase was extracted with diethyl ether (3 ꢂ 20 ml). After drying
the combined organic extracts (Na2SO4), filtration, and evaporation
R = Me (1a), i-Pr (1b). To the respective alcohol ROH (200 ml)
sodium hydride (7.9 g, 0.28 mol) was added slowly. When no fur-
ther H2 was liberated, PhSCH2CH2CH2Br (57.8 g, 0.25 mol) was
added and the reaction mixture was refluxed for 6 h and stirred
at room temperature overnight. The reaction mixture was diluted
with water (200 ml), extracted with diethyl ether (3 ꢂ 80 ml) and
the combined organic extracts were dried (Na2SO4). After filtration
and evaporation of the solvent under reduced pressure the residue
was distilled in vacuo.
of the solvents the
by integration of the requisite 119Sn NMR signals. In the case of 3a–
c the -products ( -3a–c) have been obtained in a pure state by
a/ortho ratios in the residues were determined
R = Me (1a). Yield: 37.3 g (82%). Bp: 115–118 °C (4 Torr). 1H
NMR (400 MHz, CDCl3): d 1.88 (m, 2H, CH2CH2CH2), 2.99 (m, 2H,
CH2SPh), 3.30 (s, 3H, OCH3), 3.46 (m, 2H, CH2OMe), 7.13–7.17 (m,
1H, p-H, SPh), 7.24–7.28 (m, 2H, m-H, SPh), 7.31–7.34 (m, 2H, o-
H, SPh). 13C NMR (100 MHz, CDCl3): d 29.5 (s, CH2CH2CH2), 30.5
(s, CH2SPh), 58.7 (s, OCH3), 71.0 (s, CH2OMe), 125.8 (s, p-C, SPh),
128.8 (s, m-C, SPh), 129.1 (s, o-C, SPh), 136.6 (s, i-C, SPh).
a
a
vacuum distillation. Due to the high boiling point
a-3d could not
be obtained in this way.
R = Me (a-3a). Yield: 3.80 g (81%). Bp: 137–141 °C (0.05 Torr).
Anal. Calc. C22H40OSSn (471.33): C, 56.06; H, 8.55. Found: C, 56.67;
H, 7.84%. 1H NMR (400 MHz, CDCl3): d 0.93 (t, 3J(H,H) = 7,47 Hz,
9H, d-CH3, Bu), 1.10–1.29 (m, 6H, a-CH2, Bu), 1.32–1.42 (m, 6H, c-
R = i-Pr (1b). Yield: 32.1 g (62%). Bp: 124 °C (5 Torr). 1H NMR
(400 MHz, CDCl3): d 1.13 (d, 3J(H,H) = 6.23 Hz, 6H, CH3), 1.86 (m,
2H, CH2CH2CH2), 3.00 (m, 2H, CH2SPh), 3.30–3.76 (m, 3H, OCH-
Me2 + CH2Oi-Pr), 7.12–7.16 (m, 1H, p-H, SPh), 7.22–7.29 (m, 2H,
m-H, SPh), 7.30–7.35 (m, 2H, o-H, SPh). 13C NMR (100 MHz, CDCl3):
d 22.1 (s, CH3), 29.7 (s, CH2CH2CH2), 30.4 (s, CH2SPh), 66.2 (s,
OCH(Me)2), 71.5 (s, CH2OCHMe2), 125.7 (s, p-C, SPh), 128.8 (s, m-
C, SPh), 129.0 (s, o-C, SPh), 136.7 (s, i-C, SPh).
R = t-Bu (1c). To a stirred mixture of tert-butanol (200 ml),
phosphoric acid (40 ml, 85%) and sodium sulfate (30 g) at 60 °C
PhSCH2CH2CH2OH (18.6 g, 0.1 mol) was added dropwise and then
the reaction mixture was refluxed for 12 h. After cooling to room
CH2, Bu), 1.54–1.70 (m, 6H, b-CH2, Bu), 1.90ꢀ1.94 (m, 2H,
CH2CH2CH), 2.98ꢀ3.05 (m + d, 2J(119Sn,H) = 52.8 Hz, 1H, SnCH),
3.04 (s, 3H, OCH3), 3.14–3.21 (m, 2H, CH2OMe), 7.49–7.53 (m, 1H,
p-H, SPh + m, 2H, m-H, SPh), 7.81–7.84 (m, 2H, o-H, SPh). 13C NMR
(125 MHz, CDCl3): d 10.2 (s + d + d, 1J(117Sn,C) = 313.8 Hz, 1J(119Sn,C) =
328.7 Hz,
a
-C, Bu), 13.7 (s, d-C, Bu), 25.1 (s + d, 1J(119Sn,C) = 250.8 Hz,
SnCH), 27.4 (s + d, 3J(119Sn,C) = 58.1 Hz,
c-C, Bu), 29.1 (s + d,
2J(119Sn,C) = 19.7 Hz, b-C, Bu), 33.4 (s, CH2CH2CH), 58.5 (s, OCH3), 71.1
(s, CH2OMe), 125.3 (s, p-C, SPh), 128.4 (s, m-C, SPh), 128.6 (s, o-C,
SPh), 138.9 (s, i-C, SPh). 119Sn NMR (186 MHz, THF-d8): d ꢀ10.7 (s).
R = i-Pr (a-3b). Yield: 3.45 g (69%). Bp: 158–161 °C (0.03 Torr).
Anal. Calc. for C24H44OSSn (499.38): C, 57.76; H, 8.82. Found: C,

3358
M. Block et al. / Journal of Organometallic Chemistry 694 (2009) 3353–3361
57.78; H, 8.33%. 1H NMR (400 MHz, CDCl3):
d
a
0.90 (t,
-CH2, Bu),
3H/3H,
7.28 (m, 2H, H5 + H3, C6H4), 7.37–7.39 (m, 1H, H6, C6H4). 13C
NMR (125 MHz, CDCl3): d 10.8 (s + d + d, 1J(117Sn,C) = 330.3 Hz,
3J(H,H) = 7.48 Hz, 9H, d-CH3, Bu), 0.97–1.01 (m, 6H,
1.09/1.10
(d/d,
3J(H,H) = 6.10 Hz/3J(H,H) = 6.10 Hz,
1J(119Sn,C) = 345.8 Hz,
a
-C, Bu), 13.6 (s, d-C, Bu), 22.0 (s,
CH2OCH(CH3)2), 1.29–1.37 (m, 6H,
c
-CH2, Bu), 1.49–1.57 (m, 6H,
CH2OCH(CH3)2), 27.3 (s + d, 3J(119Sn,C) = 60.7 Hz,
c-C, Bu), 29.0
b-CH2, Bu), 2.04–2.08 (m, 2H, CH2CH2CH), 3.06 (m + d,
2J(119Sn,H) = 52.0 Hz, 1H, SnCH), 3.41–3.48 (m, 1H + 2H,
CH2OCH(CH3)2 + CH2Oi-Pr), 7.10–7.14 (m, 1H, p-H, SPh), 7.23–
7.27 (m, 2H, m-H, SPh), 7.34–7.36 (m, 2H, o-H, SPh). 13C NMR
(s + d, 2J(119Sn,C) = 19.6 Hz, b-C, Bu), 29.8 (s, CH2CH2CH2), 32.3 (s,
PhSCH2), 66.3 (s, CH2OCH(CH3)2), 71.3 (s, CH2OCH(CH3)2), 125.4
(s, C6, C6H4), 128.6/128.7/136.5 (s, C3, C6H4) (s/s/s, C3,C4,C5,
C6H4), 144.6 (s + d, 2J(119Sn,C) = 23.1 Hz, C2–S, C6H4), 145.8 (s + d,
1J(119Sn,C) = 391.3 Hz, C1–Sn, C6H4). 119Sn NMR (186 MHz, CDCl3):
d ꢀ43.4 (s).
(125 MHz, CDCl3):
d
a
10.0 (s + d + d, 1J(117Sn,C) = 311.2 Hz,
-C, Bu), 13.7 (s, d-C, Bu), 22.0/22.2 (s/s,
1J(119Sn,C) = 325.9 Hz,
CH2OCH(CH3)2), 24.9 (s + d, 1J(119Sn,C) = 249.2 Hz, SnCH), 27.4
R = t-Bu, o-3c: 1H NMR (400 MHz, CDCl3):
3J(H,H) = 7.30 Hz, 9H, d-CH3, Bu), 0.92–0.96 (m, 6H,
d
0.92 (t,
(s + d,
3J(119Sn,C) = 58.8 Hz,
c
-C,
Bu),
29.1
(s + d,
a-CH2, Bu),
2J(119Sn,C) = 19.7 Hz, b-C, Bu), 34.3 (s, CH2CH2CH), 66.9 (s + d,
3J(119Sn,C) = 20.7 Hz, CH2OCH(CH3)2), 71.5 (s, CH2OCH(CH3)2),
125.3 (s, p-C, SPh), 128.4 (s, m-C, SPh), 128.6 (s, o-C, SPh), 139.1
(s, i-C, SPh). 119Sn NMR (186 MHz, CDCl3): d ꢀ9.7 (s).
1.20 (s, 9H, CH2OC(CH3)3), 1.34–1.39 (m, 6H, c-CH2, Bu), 1.54–
1.62 (m, 6H, b-CH2, Bu),1.84–1.91 (m, 2H, CH2CH2CH2), 3.02 (m,
2H, PhSCH2), 3.46 (m, 2H, CH2Ot-Bu), 7.11–7.17 (m, 1H, H4,
C6H4), 7.23–7.28 (m, 2H, H5 + H3, C6H4), 7.38–7.40 (m, 1H, H6,
R = t-Bu (a-3c). Yield: 2.58 g (49%). Bp: 176 °C (0.01 Torr). Anal.
C6H4). 13C NMR (125 MHz, CDCl3):
1J(117Sn,C) = 330.4 Hz, 1J(119Sn,C) = 345.8 Hz,
Bu), 27.3 (s + d, 3J(119Sn,C) = 60.8 Hz,
d
a
10.8 (s + d + d,
-C, Bu), 13.6 (s, d-C,
c-C, Bu), 27.4 (s,
Calc. for C25H46OSSn (513.05): C, 58.82; H, 9.30. Found: C, 58.52; H,
8.97%. 1H NMR (400 MHz, CDCl3): d 0.79 (t, 3J(H,H) = 7.26 Hz, 9H, d-
CH3, Bu), 0.86–0.90 (m, 6H,
1.18–1.27 (m, 6H,
a
-CH2, Bu), 1.02 (s, 9H, CH2OC(CH3)3),
CH2OC(CH3)3), 29.1 (s + d, 2J(119Sn,C) = 19.6 Hz, b-C, Bu), 31.5 (s,
CH2CH2CH2), 32.3 (s, PhSCH2), 59.9 (s, CH2OC(CH3)3), 72.5 (s,
CH2OC(CH3)3), 125.3 (s, C6, C6H4), 128.68/128.75/136.5 (s/s/s,
C3,C4,C5, C6H4), 144.8 (s + d, 2J(119Sn,C) = 23.2 Hz, C2–Sn, C6H4),
145.8 (s, C1–Sn, C6H4). 119Sn NMR (186 MHz, CDCl3): d ꢀ43.6 (s).
c
-CH2, Bu), 1.39–1.47 (m, 6H, b-CH2, Bu), 1.91–
1.95 (m, 2H, CH2CH2CH), 2.95 (m + d, 2J(119Sn,H) = 52.3 Hz, 1H,
SnCH), 3.17–3.23/3.25–3.32 (m/m, 1H/1H, CH2Ot-Bu), 7.01–7.02
(m, 1H, p-H, SPh), 7.11–7.15 (m, 2H, m-H, SPh), 7.24–7.26 (m, 2H,
o-H, SPh). 13C NMR (100 MHz, CDCl3):
d
10.0 (s + d + d,
-C, Bu), 13.6 (s, d-C,
Bu), 24.9 (s + d, 1J(119Sn,C) = 247.5 Hz, SnCH), 27.5 (s + d,
1J(117Sn,C) = 310.8 Hz, 1J(119Sn,C) = 325.6 Hz,
a
3.4.1. NMR experiments
In a Schlenk tube the solvent of a solution of n-BuLi (ca
0.5 mmol) in n-hexane was removed in vacuo. To the residue a
1:1 mixture of the requisite sulfide 1b/1c (0.5 mmol) and tmeda
(0.5 mmol) in benzene-d6 (ca 0.5 ml) was added via a syringe. Then
the reaction mixture was transferred to a NMR tube which was
sealed by melting.
[Li(o-C6H4SCH2CH2CH2OR)(tmeda)] (R = i-Pr, o-2b; t-Bu, o-2c).
R = i-Pr (o-2b). 13C NMR (50 MHz, benzene-d6): d 22.0 (s,
OCH(CH3)2), 30.4 (s, CH2CH2CH2), 34.0 (s, PhSCH2), 46.1 (s, NCH3,
tmeda), 56.9 (s, CH2N, tmeda), 66.9 (s, CH2Oi-Pr), 71.4 (s,
OCH(CH3)2), 121.6/122.3/125.5/141.8 (s/s/s/s, C6H4), 151.1 (s, C–S,
C6H4), C–Li not found due to bad signal-to-noise ratio.
R = t-Bu (o-2c). 13C NMR (50 MHz, benzene-d6): d 27.0 (s,
OC(CH3)3), 30.9 (s, CH2CH2CH2), 34.6 (s, PhSCH2), 46.0 (s, NCH3,
tmeda), 57.4 (s, CH2N, tmeda), 60.6 (s, CH2Ot-Bu), 73.4 (s,
OC(CH3)3), 119.3/121.5/125.1/141.4 (s/s/s/s, C6H4), 152.0 (s, C–S,
C6H4), 186.1 (s, C–Li, C6H4).
3J(119Sn,C) = 57.5 Hz,
c
-C, Bu), 27.6 (s, CH2OC(CH3)3), 29.0 (s + d,
2J(119Sn,C) = 20.6 Hz, b-C, Bu), 34.9 (s, CH2CH2CH), 60.8 (s, CH2Ot-
Bu), 72.6 (s, CH2OC(CH3)3), 125.3 (s, p-C, SPh), 128.4 (s, m-C, SPh),
128.5 (s, o-C, SPh), 139.1 (s, i-C, SPh). 119Sn NMR (186 MHz, CDCl3):
d ꢀ9.5 (s).
R = CPh3. 119Sn NMR (186 MHz, CDCl3):
a-3d d –9.7 (s); o-3d d –
43.6 (s).
3.4. Ortho-stannylated and -lithiated sulfides
Ortho-stannylated enriched mixtures of o-3a (o:
a = 60–80:
40–20), o-3b (o: = 50:50) and o-3c (o-3c: -3c:1c = 3:1:10) were
a
a
prepared by lithiation of 1a (lithiation time: 30 min), 1b and 1c
(lithiation times: 3 h), respectively, as described above followed
by a subsequent chromatographic work-up using preparative
centrifugally accelerated thin layer chromatography (eluent: n-
pentane).
n-Bu3Sn(o-C6H4SCH2CH2CH2OR) (R = Me, o-3a; i-Pr, o-3b; t-Bu,
o-3c).
3.5. Preparation of [Li{CH(SPh)CH2CH2OR}(tmeda)] (R = Me,
Pr, -2b; t-Bu, -2c)
a-2a; i-
a
a
R = Me, o-3a: 1H NMR (400 MHz, CDCl3):
3J(H,H) = 7,33 Hz, 9H, d-CH3, Bu), 0.99–1.23 (m, 6H,
d
0.95 (t,
a-CH2, Bu),
At ꢀ78 °C to a stirred solution of n-BuLi (0.01 mol, 1.5 M in n-
1.35–1.43 (m, 6H,
c-CH2, Bu), 1.54–1.70 (m, 6H, b-CH2, Bu),
hexane) and tmeda (1.16 g, 0.01 mol) in n-pentane (20 ml) the
respective tin compound 3a–c (0.01 mol) was added slowly via a
syringe. The reaction mixture was stirred for 2 h at this tempera-
ture and then stirred overnight at room temperature. The yellow-
ish precipitate was filtered off, washed with cold n-pentane
(4 ꢂ 10 ml) and dried in vacuo.
1.86ꢀ1.96 (m, 2H, CH2CH2CH2), 3.00 (m, 2H, PhSCH2), 3.30 (s, 3H,
OCH3), 3.45 (m, 2H, CH2OMe), 7.11–7.15 (m, 1H, H4, C6H4), 7.22–
7.26 (m, 2H, H5 + H3, C6H4), 7.35–7.39 (m, 1H, H6, C6H4). 13C
NMR (125 MHz, CDCl3): d 10.7 (s + d + d, 1J(117Sn,C) = 330.3 Hz,
1J(119Sn,C) = 345.7 Hz,
3J(119Sn,C) = 60.5 Hz,
a
-C, Bu), 13.5 (s, d-C, Bu), 27.2 (s + d,
c
-C, Bu), 28.9 (s + d, 2J(119Sn,C) = 19.5 Hz, b-
R = Me (a
-2a). Yield: 2.68 g (88%). 1H NMR (400 MHz, THF-d8): d
C, Bu), 29.1 (s, CH2CH2CH2), 30.0 (s, PhSCH2), 58.2 (s, OCH3), 70.6
(s, CH2OMe), 125.5 (s, C6, C6H4), 128.6/128.7/136.5 (s/s/s,
C3,C4,C5, C6H4), 144.4 (s + d, 2J(119Sn,C) = 23.0 Hz, C2–S, C6H4),
145.7 (s + d, 1J(119Sn,C) = 392.8 Hz, C1–Sn, C6H4). 119Sn NMR
(186 MHz, CDCl3): d ꢀ43.5 (s).
0.88–0.92 (m, 1H, CHLi), 2.12 (s, br, 2H, CH2CH2 CHLi), 2.16 (s, 12H,
CH2N(CH3)2, tmeda), 2.31 (s, 4H, CH2N(CH3)2, tmeda), 3.35 (s, 3H,
CH3O), 3.49 (s, br, 2H, CH3OCH2), 6.68–6.72 (m, 1H, p-H, SPh),
6.96–7.00 (m, 2H, m-H, SPh), 7.10–7.12 (m, 2H, o-H, SPh). 13C
NMR (100 MHz, THF-d8): d 15.5 (s, LiCH), 36.1 (s, CHCH2CH2),
46.2 (s, N(CH3)2 tmeda), 58.5 (s, CH2OCH3), 58.8 (s, CH2N tmeda),
76.4 (s, CH2OMe), 121.3 (s, p-C, SPh), 125.5 (s, o-C, SPh), 127.8 (s,
m-C, SPh), 152.1 (s, i-C, SPh).
R = i-Pr, o-3b:1H NMR (400 MHz, CDCl3):
d
0.91 (t,
3J(H,H) = 7.30 Hz, 9H, d-CH3, Bu), 0.92–0.96 (m, 6H,
a
-CH2, Bu),
1.16 (d, 3J(H,H) = 6.18 Hz, 6H, CH2OCH(CH3)2), 1.34–1.39 (m, 6H,
c-CH2, Bu), 1.54–1.62 (m, 6H, b-CH2, Bu), 1.86–1.95 (m, 2H,
R = i-Pr (
0.88–0.92 (m, 1H, CHLi), 1.18 (d, 3J(H,H) = 6.02 Hz, 6H,
OCH(CH3)2), 2.14 (s, br, 2H, CH2CH2CHLi), 2.15 (s, 12H, NCH3, tme-
a
-2b). Yield: 1.54 g (51%). 1H NMR (400 MHz, THF-d8):
CH2CH2CH2), 3.02 (m, 2H, PhSCH2), 3.49–3.57 (m, 1H + 2H,
CH2OCH(CH3)2 + CH2Oi-Pr), 7.11–7.16 (m, 1H, H4, C6H4), 7.24–
d

M. Block et al. / Journal of Organometallic Chemistry 694 (2009) 3353–3361
3359
da), 2.31 (s, 4H, CH2N, tmeda), 3.57 (s, br, 2H, CH2Oi-Pr), 3.66 (quin,
3J(H,H) = 6.02 Hz, 1H, OCH(CH3)2), 6.69–6.71 (m, 1H, p-H, SPh),
6.95–6.99 (m, 2H, m-H, SPh), 7.10–7.12 (m, 2H, o-H, SPh). 13C
NMR (100 MHz, THF-d8): d 15.8 (s, CHLi), 22.4 (s, OCH(CH3)2),
36.6 (s, CH2CH2CHLi), 46.2 (s, NCH3, tmeda), 58.9 (s, CH2N, tmeda),
71.5 (s, CH2Oi-Pr), 72.5 (s, OCH(CH3)2), 121.2 (s, p-C, SPh), 125.5 (s,
m-C, SPh), 127.8 (s, p-C, SPh), 152.3 (s, i-C, SPh).
7.89 (m, 2H, o-H, SO2Ph). 13C NMR (125 MHz, CDCl3): d 21.9 (s,
CH2OCH(CH3)2), 23.6 (s, CH2CH2CH2), 53.6 (s, CH2SO2Ph), 65.4 (s,
CH2Oi-Pr), 71.6 (s, CH2OCH(CH3)2), 128.0 (s, o-C, SO2Ph), 129.2 (s,
o-C, SO2Ph), 133.6 (s, p-C, SO2Ph), 139.2 (s, i-C, SO2Ph).
3.8. Preparation of PhSO2CH2CH2CH2OCPh3 (5c)
R = t-Bu (
a
-2c). Yield: 3.06 g (89%). 1H NMR (500 MHz, THF-d8):
At room temperature to a stirred solution of PhSO2CH2CH2-
CH2OH (5.0 g, 0.03 mol) and Ph3CCl (8.4 g, 0.03 mol) in dichloro-
methane (150 ml), 1,8-diazabicyclo[5.4.0]undec-7-ene (5.3 g,
0.04 mol) was added dropwise. After stirring for 2 days at this tem-
perature, the solution was diluted with water (300 ml). The aque-
ous phase was extracted with dichloromethane (3 ꢂ 150 ml) and
the combined organic extracts were dried (Na2SO4). After filtration
and evaporation of the solvent under reduced pressure the residue
was purified by means of column chromatography (silica; n-pen-
tane/diethyl ether 3:1). Yield: 5.1 g (46%).
d 0.89 (m, 1H, CHLi), 1.15 (s, 9H, (CH3)3CO), 2.15 (s, 12H,
CH2N(CH3)2, tmeda), 2.31 (s, 4H CH2N(CH3)2, tmeda), 2.49 (s, br,
2H, CH2CH2CHLi), 3.51 (s, br, 2H, CH2Ot-Bu), 6.65–6.69 (m, 1H, p-
H, SPh), 6.95–6.99 (m, 2H, m-H, SPh), 7.09–7.12 (m, 2H, o-H,
SPh). 13C NMR (100 MHz, benzene-d6):
d
15.8 (s,
1J(13C,1H) = 130 Hz, CHLi), 27.8 (s, (CH3)3CO), 36.9 (s, CH2CH2CHLi),
46.2 (s, CH2N(CH3)2, tmeda), 58.9 (s, CH2N(CH3)2, tmeda), 64.7 (s,
(CH3)3CO), 74.1 (s, CH2Ot-Bu), 121.2 (s, p-C, SPh), 129.5 (s, m-C,
SPh), 129.5 (s, o-C, SPh), 152.4 (s, i-C, SPh).
1H NMR (400 MHz, CDCl3): d 1.91–1.98 (m, 2H, CH2CH2CH2),
3.12 (m, 2H, CH2OCPh3), 3.18–3.21 (m, 2H, CH2SO2Ph), 7.05–7.28
(m, 3H + 6H, p-H + m-H, CPh3), 7.29–7.39 (m, 6H, o-H, CPh3),
7.52–7.56 (m, 2H, m-H, SO2Ph), 7.62–7.66 (m, 1H, p-H, SO2Ph),
7.87–7.90 (m, 2H, o-H, SO2Ph). 13C NMR (100 MHz, CDCl3): d 23.8
(s, CH2CH2CH2), 53.9 (s, CH2SO2Ph), 61.5 (s, CH2OCPh3), 86.8 (s,
OCPh3), 127.1 (s, p-C, CPh3), 127.8 (s, m-C, CPh3), 128.1 (s, o-C,
SO2Ph), 128.5 (s, o-C, CPh3), 129.3 (s, m-C, SO2Ph), 133.6 (s, p-C,
SO2Ph), 139.1 (s, i-C, SO2Ph), 143.8 (s, i-C, CPh3).
3.6. Preparation of [Li{CH(SPh)CH2CH2OR}] (R = Me, a-4a; i-Pr, a-4b)
At ꢀ78 °C to a stirred solution of n-BuLi (0.01 mol, 1.5 m in n-
hexane) in n-pentane (20 ml) the respective tin compound 3a–b
(0.01 mol) was added slowly via a syringe. The reaction mixture
was stirred for 2 h at this temperature and then stirred overnight
at room temperature. The yellowish precipitate was filtered off,
washed with n-pentane (4 ꢂ 10 ml) and dried in vacuo.
R = Me (a
-4a). Yield: 1.69 g (90%). 1H NMR (200 MHz, THF-d8): d
0.86–0.90 (m, br, CHLi), 2.08–2.15 (m, br, 2H, CH2CH2CHLi), 3.35 (s,
3H, CH3O), 3.49 (s, br, 2H, CH2OMe), 6.66–6.74 (m, 1H, p-H, SPh),
6.94–7.10 (m, 2H, m-H, SPh), 7.12–7.14 (m, 2H, o-H, SPh). 13C
NMR (50 MHz, THF-d8): d 15.35 (s, CHLi), 36.1 (s, CH2CH2CHLi),
58.5 (s, CH3O), 76.3 (s, CH3OMe), 121.3 (s, p-C, SPh), 125.5 (o-C,
SPh), 127.8 (s, m-C, SPh), 152.1 (s, i-C, SPh).
3.9. Preparation of Li[CH(SO2Ph)CH2CH2OR] (R = Me, 6a; i-Pr, 6b;
CPh3, 6c)
At room temperature to a stirred solution of n-BuLi (0.01 mol,
1.5 M in n-hexane) in n-pentane (20 ml) (or toluene in the case
of 6c) the respective sulfone 5aꢀc (0.01 mol) was added slowly
via a syringe. After stirring for 24 h the yellowish precipitate was
filtered off, washed with n-pentane (3 ꢂ 10 ml) and dried in vacuo.
R = Me (6a). Yield: 1.78 g (81%). 1H NMR (400 MHz, DMSO-d6): d
1.74 (m, 1H, CH2CH2CH), 1.89 (m, 2H, CH2CH2CH), 2.98 (m, 2H,
CH2OMe), 3.07 (s, 3H, OCH3), 7.04–7.09 (m, 1H, p-H, SO2Ph),
7.17–7.20 (m, 2H, m-H, SO2Ph), 7.49–7.50 (m, 2H, o-H, SO2Ph).
13C NMR (100 MHz, THF-d8): d 28.2 (s, CH2CH2CH), 42.8 (s,
1J(13C,1H) = 147 Hz, CH2CH2CH), 58.6 (s, OCH3), 76.3 (s, CH2OMe),
125.9 (s, o-C, SO2Ph), 127.1 (s, m-C, SO2Ph), 128.5 (s, p-C, SO2Ph),
152.4 (s, i-C, SO2Ph).
R = i-Pr (
a
-4b). Yield: 1.90 g (90%). 1H NMR (400 MHz, THF-d8):
3
d
0.83–0.93 (m, 1H, CHLi), 1.17 (d, JH,H = 6.23 Hz, 6H,
CH2OCH(CH3)2), 2.13 (s, br, 2H, CH2CH2CHLi), 3.53 (s, br, 2H,
3
CH2Oi-Pr), 3.61 (sept, JH,H = 6.02 Hz, 1H, CH2OCH(CH3)2), 6.66–
6.71 (m, 1H, p-H, SPh), 6.91–7.09 (m, 2H, m-H, SPh), 7.11–7.16
(m, 2H, o-H, SPh). 13C NMR (100 MHz, THF-d8): d 15.7 (s, CHLi),
22.4/22.4 (s/s, CH2OCH(CH3)2), 36.6 (s, CH2CH2CHLi), 71.4 (s,
CH2Oi-Pr), 72.5 (s, CH2OCH(CH3)2), 121.2 (s, p-C, SPh), 125.4 (s, o-
C, SPh), 127.7 (s, m-C, SPh), 152.3 (s, i-C, SPh).
3.7. Preparation of PhSO2CH2CH2CH2OR (R = Me, 5a; i-Pr, 5b)
R = i-Pr (6b). Yield: 1.96 g (79%). 1H NMR (400 MHz, DMSO-d6):
d 0.95 (d, 3J(H,H) = 6.02 Hz, 6H, OCH(CH3)2), 1.70 (s, br, 1H,
CH2CH2CH), 1.87 (m, 2H, CH2CH2CH), 2.98 (m, 2H, CH2Oi-Pr),
3.34 (m, 1H, OCH(CH3)2), 7.05–7.09 (m, 2H, m-H, SO2Ph), 7.17–
7.19 (m, 2H + 1H, o-H + pH, SO2Ph). 13C NMR (100 MHz, DMSO-
d6): d 22.0 (s, OCH(CH3)2), 28.5 (s, CH2CH2CH), 42.2 (s, CH2CH2CH),
69.6 (s, CH2Oi-Pr),71.1 (s, OCH(CH3)2), 125.8 (s, o-C, SO2Ph), 127.2
(s, m-C, SO2Ph), 129.2 (s, p-C, SO2Ph), 155.4 (s, i-C, SO2Ph).
R = CPh3 (6c). Yield: 3.5 g (78%). 1H NMR (400 MHz, DMSO-d6):
d 1.75 (s, br, 1H, CH2CH2CH), 2.11 (s, br, 2H, CH2CH2CH), 2.29 (s, br,
2H, CH2OCPh3) 7.05–7.30 (m, br, 5H + 15H, p-, m-, o-H, SO2Ph + p-,
To a stirred mixture of the sulfide 1a or 1b (0.05 mol) in acetic
acid (150 ml), H2O2 (40 ml, 30% in water) was added dropwise.
After stirring for 4 h at room temperature and for 30 min at
90 °C, the reaction mixture was poured on ice (100 g). The aqueous
phase was extracted with toluene (4 ꢂ 10 ml). The combined or-
ganic phases were dried (Na2SO4) and after filtration the solvents
were evaporated under reduced pressure. The residues proved to
be pure (>98%) and were used without further purification.
R = Me (5a). Yield: 9.9 g (93%). 1H NMR (400 MHz, CDCl3): d
1.96–1.98 (m, 2H, CH2CH2CH2), 3.14–3.22 (m, 2H, CH2SO2Ph),
3.23 (s, 3H, OCH3), 3.36–3.39 (m, 2H, CH2OMe), 7.51–7.55 (m,
2H, m-H, SO2Ph), 7.59–7.64 (m, 1H, p-H, SO2Ph), 7.86–7.89 (m,
2H, o-H, SO2Ph). 13C NMR (100 MHz, CDCl3): d 23.3 (s, CH2CH2CH2),
53.6 (s, 1J(13C,1H) = 137 Hz, CH2SO2Ph), 58.6 (s, CH2OMe), 70.2
(s,CH3O), 128.0 (s, o-C, SO2Ph), 129.2 (s, m-C, SO2Ph), 133.6 (s, p-
C, SO2Ph), 139.2 (s, i-C, SO2Ph).
m-, o-H, OCPh3). 13C NMR (100 MHz, DMSO-d6):
d 21.0 (s,
CH2CH2CH), 45.2 (s, CH2CH2CH), 67.0 (s, CH2OCPh3), 85.2 (s,
OCPh3), 125.1 (s, p-C, CPh3), 127.5 (s, m-C, CPh3), 128.0 (s, m-C,
SO2Ph), 128.1 (s, o-C, CPh3), 128.7 (s, o-C, SO2Ph), 137.2 (s, p-C,
SO2Ph), 144.5 (s, i-C, CPh3), 155.8 (s, i-C, SO2Ph).
3.10. Preparation of n-Bu3SnCH(SO2Ph)CH2CH2OR (R = Me, 7a; i-Pr,
7b; CPh3, 7c)
R = i-Pr (5b). Yield: 9.1 g (88%). 1H NMR (400 MHz, CDCl3): d
1.05 (d, 3J(H,H) = 6,10 Hz, 6H, CH2OCH(CH3)2), 1.88–1.94 (m, 2H,
CH2CH2CH2), 3.15–3.18 (m, 2H, CH2SO2Ph), 3.37–3.41 (m, 2H,
CH2Oi-Pr), 3.44 (qui, 3J(H,H) = 6,10 Hz, 1H, CH2OCH(CH3)2), 7.51–
7.54 (m, 2H, m-H, SO2Ph), 7.59–7.63 (m, 1H, p-H, SO2Ph), 7.86–
At room temperature to a stirred solution of n-BuLi (0.01 mol,
1.5 M in n-hexane) in n-pentane (20 ml) (or toluene in the case
of 7c) the respective sulfone 5aꢀc (0.01 mol) was added. After

3360
M. Block et al. / Journal of Organometallic Chemistry 694 (2009) 3353–3361
24 h n-Bu3SnCl (3.2 g, 0.01 mol) was added slowly. To the suspen-
sion obtained water was added (15 ml) and the aqueous phase was
extracted with diethyl ether (3 ꢂ 15 ml). After drying the com-
bined organic extracts (Na2SO4) and filtration the solvent was
evaporated. The residues were purified by preparative centrifugal
thin layer chromatography (silica; n-pentane/diethyl ether 3:1).
R = Me (7a). Yield: 3.12 g (62%). Anal. Calc. for C22H40O3SSn
(503.02): C, 52.47; H, 7.95. Found: C, 52.11; H, 7.53%. 1H NMR
(500 MHz, CDCl3): d 0.91 (t, 3J(H,H) = 7.33 Hz, 9H, d-CH3, Bu),
OCPh3), 7.33–7.45 (m, 2H, m-H, SO2Ph), 7.52–7.55 (m, 1H, p-H,
SO2Ph), 7.79–7.81 (m, 2H, p-H, SO2Ph). 13C NMR (125 MHz, CDCl3):
d 11.5 (s + d + d, 1J(117Sn,C) = 319.8 Hz, 1J(119Sn,C) = 337,0 Hz,
a-C,
Bu), 13.6 (s, d-C, Bu), 22.6 (s, CH2CH2CHSn), 27.2 (s + d,
2J(119Sn,C) = 63.6 Hz, b-C, Bu), 28.8 (s + d, 3J(119Sn,C) = 19.4 Hz,
c-
C, Bu), 51.0 (s + d, 1J(119Sn,C) = 126.4 Hz, CHSn), 62.1 (s, CH2OCPh3),
86.6 (s, OCPh3), 127.0 (s, p-C, OCPh3), 127.7 (s, m-C, OCPh3), 127.9
(s, o-C, SO2Ph), 128.4 (s, o-C, OCPh3), 128.7 (s, m-C, SO2Ph), 132.4 (s,
p-C, SO2Ph), 140.9 (s, i-C, SO2Ph), 143.8 (s, i-C, OCPh3). 119Sn NMR
(186 MHz, CDCl3): d 2.7 (s).
1.12–1.19 (m, 6H,
a-CH2, Bu), 1.33–1.39 (m, 6H, c-CH2, Bu),
1.53–1.62 (m, 6H, b-CH2, Bu), 1.92–1.96 (m, 2H, CH2CH2CHSn),
3.03–3.06 (m + d, 2J(119Sn,H) = 140.9 Hz, 1H, SnCH), 3.05 (s, 3H,
CH3O), 3.06–3.12 (m, 2H, CH2OMe), 7.47–7.50 (m, 2H, m-H, SO2Ph),
7.53–7.55 (m, 1H, p-H, SO2Ph), 7.82–7.84 (m, 2H, o-H, SO2Ph). 13C
NMR (100 MHz, CDCl3): d 11.9 (s + d + d, 1J(117Sn,C) = 323.9 Hz,
3.11. X-ray crystallography
Data for X-ray diffraction analysis of single crystals of
tained from n-pentane solution at ꢀ10 °C, were collected at
130(2) K on a CCD Oxford Xcalibur S (k(Mo K ) = 0.71073 Å) in
and u scans mode. A summary of the crystallographic data, the
data collection parameters, and the refinement parameters is given
in Table 5. Semi-empirical from equivalents absorption corrections
a-2c, ob-
1J(119Sn,C) = 338.9 Hz,
a
-C, Bu), 13.7 (s, d-C, Bu), 27.3 (s + d,
2J(119Sn,C) = 63.9 Hz, b-C, Bu), 27.9 (s, CH2CH2CHSn), 28.9 (s + d,
3J(119Sn,C) = 19.4 Hz, -C, Bu), 50.9 (s + d, 1J(119Sn,C) = 129.3 Hz,
a
x
c
CHSn), 58.3 (s, CH2OMe), 70.4 (s, OCH3), 127.6 (s, o-C, SO2Ph),
128.9 (s, m-C, SO2Ph), 132.4 (s, p-C, SO2Ph), 141.2 (s, i-C, SO2Ph).
119Sn NMR (186 MHz, CDCl3): d 2.6 (s).
R = i-Pr (7b). Yield: 2.49 g (50%). Anal. Calc. for C24H44O3SSn
(531.04): C, 54.28; H, 8.29. Found: C, 53.95; H, 8.64%. 1H NMR
(500 MHz, CDCl3): d 0.90 (t, 3J(H,H) = 7,47 Hz, 9H, d-CH3, Bu),
0.93/0.97 (d/d, 3J(H,H) = 6.23 Hz, 3H + 3H, OCH(CH3)2), 1.12–1.20
were carried out with SCALE3 ABSPACK [30]. The structure was solved
with direct methods [31]. Structure refinement was carried out
using full-matrix least-square routines against F2 with SHELXL-97
[32]. All non-hydrogen atoms were refined anisotropically; hydro-
gen atoms were placed in calculated positions and refined with cal-
culated isotropic displacement parameters.
(m, 6H,
a-CH2, Bu), 1.21–1.39 (m, 6H, c-CH2, Bu), 1.49–1.64 (m,
6H, b-CH2, Bu), 1.92–1.96 (m, 2H, CH2CH2CHSn), 2.97–3.10 (m,
2H + 1H, CH2Oi-Pr + CHSn), 3.22 (quin, 3J(H,H) = 6.02 Hz, 1H,
OCH(CH3)2), 7.46–7.56 (m, 2H, m-H, SO2Ph + m, 1H, p-H, SO2Ph),
7.82–7.84 (m, 2H, p-H, SO2Ph). 13C NMR (125 MHz, CDCl3): d 11.7
Acknowledgements
Financial support from the Deutsche Forschungsgemeinschaft
and gifts of chemicals from Merck (Darmstadt) are gratefully
acknowledged.
(s + d + d, 1J(117Sn,C) = 322.5 Hz, 1J(119Sn,C) = 337.6 Hz,
a-C, Bu),
13.7 (s, d-C, Bu), 21.9/21.9 (s/s, OCH(CH3)2), 27.3 (s + d,
2J(119Sn,C) = 65,9 Hz, b-C, Bu), 28.3 (s, CH2CH2CHSn), 28.8 (s + d,
Appendix A. Supplementary material
3J(119Sn,C) = 19.4 Hz, -C, Bu), 50.9 (s + d + d, 1J(117Sn,C) = 128.6 Hz,
c
1J(119Sn,C) = 134.5 Hz, CHSn), 65.9 (s + d, 3J(119Sn,C) = 15.2 Hz,
CH2Oi-Pr), 71.3 (s, OCH(CH3)2), 127.7 (s, o-C, SO2Ph), 128.9 (s, m-
C, SO2Ph), 132.4 (s, p-C, SO2Ph), 141.3 (s, i-C, SO2Ph). 119Sn NMR
(186 MHz, CDCl3): d 3.7 (s).
CCDC 709946 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Center via <http://www.ccdc.ca-
m.ac.uk/data_request/cif>.
R = CPh3 (7c). Yield: 3.07 g (42%). Anal. Calc. for C40H52O3SSn
(731.20): C, 65.70; H, 7.11. Found: C, 67.38; H, 7.10%. 1H NMR
(500 MHz, CDCl3): d 0.90 (t, 3J(H,H) = 7,33 Hz, 9H,, d-CH3, Bu),
References
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a-CH2, Bu), 1.22–1.36 (m, 6H, c-CH2, Bu),
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1.48–1.55 (m, 6H, b-CH2, Bu), 2.02–2.11 (m, 2H, CH2CH2CHSn),
2.68–2.73/2.86–2.90 (m/m, 1H/1H, CH2OCPh3), 3.12 (m, 1H, CHSn),
7.19–7.27 (m, 6H + 6H, m-H + o-H, OCPh3), 7.28–7.32 (m, 3H, p-H,
[2] M. Schöllkopf, A. Lerch, Angew. Chem. 73 (1961) 27.
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(2000) 2829–2831.
Table 5
Crystallographic data for of [Li{CH(SPh)CH2CH2Ot-Bu}(tmeda)] (
a
-2c).
Empirical formula
Mr
C19H35LiN2OS
346.49
Crystal system
monoclinic
P21/c
Space group
0
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(1988) 1259–1262.
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(2004) 3668–3673.
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in: M. Melnik, J. Sima, M. Tatarko (Eds.), Advances in Coordination,
Bioinorganic and Inorganic Chemistry, vol. 170, STU Press, Bratislava, 2005.
[14] M. Linnert, Ph.D. Thesis, Martin-Luther-Universität Halle-Wittenberg, 2006.
[15] D.A. Shirley, B.J. Reeves, J. Organomet. Chem. 16 (1969) 1–6.
[16] T. Al-Allaf, J. Organomet. Chem. 306 (1986) 337–346.
[17] B. Wrackmeyer, Annu. Rep. NMR-Spectrosc. 16 (1985) 73–186.
[18] T. Rüffer, Ph.D. Thesis, Martin-Luther-Universität Halle-Wittenberg, 1999.
[19] Y. Ura, R. Hara, T. Takahashi, J. Organomet. Chem. 611 (2000) 299–303.
[20] (a) G. Chassaing, A. Marquet, Tetrahedron 34 (1978) 1399–1404;
(b) J. Gabriel, D. Seebach, Helv. Chim. Acta 67 (1984) 1070–1082;
(c) D. Seebach, J. Gabriel, R. Hässig, Helv. Chim. Acta 67 (1984) 1083–1099.
a (AÅ)
14.578(5)
12.880(3)
13.397(4)
2138(1)
0
b (AÅ)
0
c (AÅ)
0
V (AÅ)
Z
4
Dcalc (g cmꢀ1
)
1.076
0.158
760
l
(Mo K
F(0 0 0)
range (°)
a
) (mmꢀ1
)
H
3.05ꢀ26.37
Reflection collected
Reflection observed [I > 2
Reflection independent
20 220
r(I)]
2570
4376 (Rint = 0.076)
4376/0/224
0.999
0.0841, 0.2277
0.1320, 0.2502
0.98/ꢀ0.36
Data/restraints/parameters
Goodness-of-fit on F2
R1, wR2 [I > 2
R1, wR2 (all data)
Largest difference in peak and hole (e ÅAꢀ3
r
(I)]
0
)

M. Block et al. / Journal of Organometallic Chemistry 694 (2009) 3353–3361
3361
[21] Cambridge Structural Database (ConQuest Version 1.10, 2008), Cambridge
Crystallographic Data Centre, University Chemical Laboratory, Cambridge, UK.
[22] (a) R. Lett, G. Chassaing, A. Marquet, J. Organomet. Chem. 111 (1976) C17–C20;
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