Facile hydroboration with the dimethylsulfide adducts of mono- and bis-(pentafluorophenyl)borane

Article abstract of DOI:10.1016/j.jorganchem.2012.07.012

The dimethylsulfide adduct of bis(pentafluorophenyl)borane HB(C ₆F₅)₂·SMe₂ reacts on mixing with alkenes such as 1-hexene and styrene, with selectivities closely following those of the Me₂S-free reagent. The mono(pentafluorophenyl)borane H₂B(C₆F₅)·SMe₂ also undergoes rapid hydroboration reactions to give the dialkylboranes R₂B(C ₆F₅). Treatment of the boranes with trimethylsilylacetylene results in rapid hydroboration to give the trans-vinylborane. The reaction of H₂B(C₆F ₅)·SMe₂ with 1,5-cyclooctadiene at room temperature yields a kinetic mixture of the 1,4- and 1,5-dihydroboration products which quantitatively isomerizes on heating to the 1,5-isomer, pentafluorophenyl-9- borobicyclo[3.3.1]nonane. This bicyclic borane crystallizes as the SMe ₂ adduct, which has been characterized by X-ray crystallography.

Full text of DOI:10.1016/j.jorganchem.2012.07.012

Journal of Organometallic Chemistry 730 (2013) 44e48
Contents lists available at SciVerse ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Facile hydroboration with the dimethylsulfide adducts of mono- and
bis-(pentafluorophenyl)boraneq
*
Elizabeth A. Jacobs, Renukadevi Chandrasekar, Dan A. Smith, Callum M. White, Manfred Bochmann ,
*
Simon J. Lancaster
Wolfson Materials and Catalysis Centre, School of Chemistry, University of East Anglia, Norwich Research Park, Norwich NR4 7TJ, UK
a r t i c l e i n f o
a b s t r a c t
Article history:
The dimethylsulfide adduct of bis(pentafluorophenyl)borane HB(C6F5)2$SMe2 reacts on mixing with
alkenes such as 1-hexene and styrene, with selectivities closely following those of the Me2S-free reagent.
The mono(pentafluorophenyl)borane H2B(C6F5)$SMe2 also undergoes rapid hydroboration reactions to
give the dialkylboranes R2B(C6F5). Treatment of the boranes with trimethylsilylacetylene results in rapid
hydroboration to give the trans-vinylborane. The reaction of H2B(C6F5)$SMe2 with 1,5-cyclooctadiene at
room temperature yields a kinetic mixture of the 1,4- and 1,5-dihydroboration products which quanti-
tatively isomerizes on heating to the 1,5-isomer, pentafluorophenyl-9-borobicyclo[3.3.1]nonane. This
bicyclic borane crystallizes as the SMe2 adduct, which has been characterized by X-ray crystallography.
Ó 2012 Elsevier B.V. All rights reserved.
Received 18 June 2012
Received in revised form
6 July 2012
Accepted 9 July 2012
Keywords:
Boranes
Hydroboration
Alkenes
Lewis adduct
11B NMR spectroscopy
1. Introduction
pentafluorophenylboranes may suffice, [HB(C6F5)2]2 has recently
been used to modify ligands, and for these and other synthetic
Since the first report of the synthesis of tris(pentafluorophenyl)
borane by Stone et al. in 1963 [1], the chemical stability and
resistance to hydrolysis have made perfluoroaryl boranes and
borates attractive reagents [2], with a wide range of uses in organic
synthesis and as catalyst activators [3,4]. While the synthesis of
B(C6F5)3 is facile [5], borane derivatives with only one or two
pentafluorophenyl groups present considerable synthetic chal-
lenges [2]. In particular, there are two reported routes to
[HB(C6F5)2]2 (1, “Piers’ borane”), neither of which is entirely
convenient, since they either require the synthesis of BCl(C6F5)2
from BCl3 and (C6F5)2SnMe2 followed by treatment with Me2SiHCl
[6], or a somewhat inefficient exchange between B(C6F5)3 and
Et3SiH [7].
applications there is a requirement for a convenient synthetic
alternative to 1 [11]. We have recently reported facile syntheses of
HB(C6F5)2∙SMe2 (1$SMe2) and H2B(C6F5)$SMe2 (2$SMe2) as crys-
talline solids [12]. These SMe2 adducts are more soluble in hydro-
carbons than base-free 1 and are easier to prepare and handle.
Herein we report the hydroboration activity of 1$SMe2 and of
2$SMe2, for which there is no base-free alternative. The double
intramolecular hydroboration reaction of 1,5-cyclooctadiene with
2$SMe2 is described, along with the crystal structure of the
resulting bicyclic alkyl borane.
2. Results and discussion
Parks et al. reported that [HB(C6F5)2]2 (1) rapidly hydroborates
alkenes and alkynes under mild conditions in near quantitative
yield, with good chemo- and regio-selectivity [8,9]. Mixtures of
B(C6F5)3 and H3B$SMe2 in hexane, thought to give 1$SMe2, have
been used to catalyze the hydroboration of alkynes with pina-
colborane [10]. While in some instances catalytic amounts of
The hydroboration activity of both 1$SMe2 and 2$SMe2 with
styrene, 1-hexene, 1,1-diphenylethylene and trimethylsilylacety-
lene have been investigated (Table 1). Initial screening reactions
were performed in an NMR tube in deuterated benzene without
heating. In the case of styrene, 1-hexene and trimethylsilylacety-
lene, hydroboration reactions proceeded quantitatively, with the
reaction being complete by the time the NMR tube was inserted
into the spectrometer. This hydroboration activity therefore closely
follows that observed by Piers et al. for the SMe2-free reagent [7].
Hydroboration reactions of the more hindered substrate 1,1-
diphenylethylene with 1$SMe2 and 2$SMe2 proceeded at a much
q
In fond memory of F. Gordon A. Stone.
* Corresponding authors.
E-mail address: s.lancaster@uea.ac.uk (S.J. Lancaster).
0022-328X/$ e see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2012.07.012

E.A. Jacobs et al. / Journal of Organometallic Chemistry 730 (2013) 44e48
45
Table 1
Hydroboration of selected alkene substrates with reagents 1$SMe2 and 2$SMe2.
Borane
Substrate
Hydroboration product
11B NMR chemical shift (ppm)
Reaction timea
1$SMe2
ꢀ1.2
<1 min
3a
1$SMe2
1$SMe2
1$SMe2
ꢀ0.5
ꢀ0.9
ꢀ3.2
<1 min
3b
<12 h
3c
<1 min
3d
2$SMe2
2$SMe2
7.1
<1 min
<1 min
4a
16
4b
2$SMe2
ꢀ6.9
<12 h
4c
2$SMe2
6.8
<1 min
4d
2$SMe2
3.8
1 h, refluxing toluene
5
a
Reactions were conducted in C6D6 at room temperature unless otherwise stated. A large excess of dimethylsulfide was added before recording the NMR spectra to drive
the dissociation equilibrium to the adducted form and facilitate a meaningful comparison of the 11B NMR chemical shifts.

46
E.A. Jacobs et al. / Journal of Organometallic Chemistry 730 (2013) 44e48
slower rate, with complete conversion requiring 12 h at room
temperature.
dimethylsulfide. The solid state structure of 5$SMe2 was deter-
mined by single crystal X-ray diffraction methods and is depicted in
Fig. 1.
The geometry at the boron center is essentially tetrahedral, with
a C(11)eB(1)eC(7) bond angle of 105.6(3)ꢁ. This is significantly
smaller than the CeBeC bond angle of 111.6(2)ꢁ for dimeric 9-BBN
[15] and is slightly larger than the BBN-cycloalkane borate anions
reported by Braunschweig et al. [16].
Minor signals were observed in the 11B NMR spectra of hydro-
boration reactions with both 1$SMe2 and 2$SMe2, which we attri-
bute to the products of slow ligand redistribution in solution.
Monitoring the 19F and 11B NMR spectra of the dihydroboration
reaction between 2$SMe2 and 1,1-diphenylethylene at hourly
intervals suggests that the second hydroboration step proceeds at
a similar rate to the first. An intermediate is observed in the 19F
3
NMR spectrum (ꢀ129.8 (m, 2F, o-F), ꢀ157.8 (t, JF,F ¼ 21 Hz, 1F, p-
3. Conclusion
F), ꢀ163.7 (m, 2F, m-F)), which is consistent with mono-
hydroboration to give (C6F5)B(H)(CHPh2), alongside resonances for
2$SMe2 and the final product. The expected doublet for the inter-
mediate was not seen in the 11B NMR spectrum, presumably
because it is obscured by resonances of the starting material and
final product.
The toluene soluble and thermally stable crystalline solids
HB(C6F5)2$SMe2 and H2B(C6F5)$SMe2 are readily prepared through
the ligand exchange reaction between B(C6F5)3 and H3B$SMe2.
These borane dimethylsulfide adducts react rapidly with unhin-
dered alkenes to give the hydroboration products under mild
conditions and in high yield. The reaction proceeds more slowly
with 1,1-disubstituted alkenes. Hydroboration of alkynes is also
possible and the stoichiometric reaction with trimethylsilylacety-
lene proceeds cleanly to give trans-alkenylboranes. The synthetic
potential of H2B(C6F5)$SMe2 is illustrated by the synthesis of pen-
tafluorophenyl-9-borabicyclo[3.3.1]nonane through the reaction
with 1,5-cyclooctadiene. Given their ease of handling, we anticipate
that these boranes will prove to be a useful addition to the arsenal
of hydroboration reagents.
2.1. Hydroboration reaction of 2$SMe2 with 1,5-cyclooctadiene
1,5-cyclooctadiene (1,5-COD) reacts with 2$SMe2 in a 1:1 M ratio
at room temperature in toluene through double hydroboration
(Scheme 1). The 11B NMR spectrum of the product shows two
signals in an approximately 2:1 ratio, consistent with the formation
of a mixture of 1,4- and 1,5- addition products, 6$SMe2 and 5$SMe2,
respectively (Scheme 1). The monohydroboration intermediate A,
was not sufficiently long-lived to be observed spectroscopically. A
similar product mixture has been reported in the hydroboration of
1,5-COD with H3B$L (L ¼ THF [13], SMe2 [14]).
4. Experimental
All synthetic procedures were carried out under dry nitrogen
using standard Schlenk-line techniques. Toluene was dried over
sodium metal and distilled prior to use. Each substrate, where
applicable, was dried over alumina prior to use. NMR samples were
prepared with deuterated benzene which had been dried over 4 Å
The 1,5-isomer 5 is thermodynamically favored and was formed
quantitatively after heating the reaction mixture in refluxing
toluene for 1 h. The adduct 5$SMe2 was isolated through recrys-
tallization of the crude product in the presence of excess
Scheme 1. Mono- and di-hydroboration of 1,5-cyclooctadiene.

E.A. Jacobs et al. / Journal of Organometallic Chemistry 730 (2013) 44e48
47
Fig. 1. ORTEP representation of 5$SMe2. Displacement ellipsoids are shown at 50% probability. Hydrogen atoms have been removed for clarity. Selected bond lengths (Å) and angles
(deg): B1eC1 1.648(5), B1eS1 2.026(4), B1eC7 1.612(5), B1eC11 1.635(5), C11eB1eC7 105.6(3), C11eB1eC1 116.3(3), C7eB1eC1 115.6(3), C7eB1eS1, 107.6(2), C11eB1eS1 105.6(2),
C1eB1eS1 105.4(2).
molecular sieves and degassed. 1H, 13C, 19F and 11B NMR spectra
were recorded using a Bruker Avance DPX300 spectrometer at
23 ꢁC. All chemical shifts are reported in parts per million and
referenced to residual solvent resonances; 19F and 11B resonances
are quoted relative to CFCl3 and BF3∙OEt2, respectively. Elemental
analyses were performed at the Department of Health and Human
Sciences, London Metropolitan University. The syntheses of 1$SMe2
and 2$SMe2 were carried out according to literature procedures
[12].
isolated base-free following essentially the same procedure. All but
3d$SMe2 and 5 were obtained as air-sensitive oils, which precluded
purification and elemental analysis.
4.1.1. (C6F5)2BCH2CH2(C6H5)∙SMe2 (3a$SMe2)
Styrene (0.14 ml, 1.2 mmol) was added dropwise with stirring to
a solution of 1$SMe2 (0.5 g, 1.2 mmol) in toluene (5 ml). The vola-
tiles were removed under reduced pressure giving the product as
a pale yellow oil in quantitative yield.
dH (300.1 MHz, C6D6): 6.8e7.2 (m, 5H, C6H5), 2.4 (m, 2H, CH2), 1.5
(t, 3JH,H ¼ 8 Hz, 2H, CH2), 1.0 (s, 6H, SMe2). dC (75.5 MHz, {1H}, C6D6):
145.9 (Cipso), 129.9 (CH), 129.2 (CH), 128.4 (CH), 33.8 (CH2), 24.5
(BCH2), 19.6 (SMe2). dF (282.4 MHz, C6D6): ꢀ130.6 (m, 4F, o-
4.1. Spectroscopic investigation of hydroborations with 1$SMe2 and
2$SMe2
3
F), ꢀ155.9 (t, JF,F ¼ 21 Hz, 2F, p-F), ꢀ162.7 (m, 4F, m-F). dB
The data in Table 1 summarize hydroboration reactions per-
formed in deuterated benzene at room temperature (unless
otherwise stated). In a typical experiment, the substrate was dis-
solved in deuterated benzene and added to an NMR tube contain-
ing a solution of the borane. The tubes were shaken to mix prior to
insertion into the spectrometer. The time taken to affect quantita-
tive hydroboration was determined by 1H, 11B and 19F NMR spec-
troscopy. In solution, there is an equilibrium between the dimethyl
sulfide adducted and dimethyl sulfide free boranes such that the 11B
NMR chemical shift is highly dependent on the amount of dime-
thylsulfide present. In order to favor the adduct and facilitate
comparison of the 11B NMR spectroscopic data an excess of dime-
thylsulfide was added to the NMR samples.
(96.3 MHz, C6D6): 0.9 (br).
4.1.2. (C6F5)B(CH2CH2(C6H5))2 (4a)
dH (300.1 MHz, C6D6): 6.9e7.3 (m, 10H, C6H5), 2.6 (t, 3JH,H ¼ 8 Hz,
4H, CH2),1.5 (t, 3JH,H ¼ 8 Hz, 4H, CH2). dC (75.5 MHz, {1H}, C6D6): 144.2
(Cipso), 129.3 (CH), 129.2 (CH), 126.8 (CH), 32.5 (BCH2), 31.5 (CH2). dF
3
(282.4 MHz, C6D6): ꢀ133.1 (m, 2F, o-F), ꢀ152.8 (t, JF,F ¼ 20 Hz, 1F,
p-F), ꢀ161.6 (m, 2F, m-F). dB (96.3 MHz, C6D6): 81.1 (br).
4.1.3. (C6F5)2B(CH2)5CH3∙SMe2 (3b$SMe2)
dH (300.1 MHz, C6D6): 1.1e1.4 (m, 10H, CH2), 1.1 (s, 6H, SMe2), 0.9
(t, 3JH,H ¼ 7 Hz, 3H, CH3). dC (75.5 MHz, {1H}, C6D6): 33.9 (CH2), 32.7
(CH2), 27.4 (CH2), 23.8 (CH2), 23.1 (BCH2), 19.6 (SMe2), 14.9 (CH3). dF
(282.4 MHz, C6D6): ꢀ130.7 (m, 4F, o-F), ꢀ155.7 (t, 3JF,F ¼ 21 Hz, 2F,
p-F), ꢀ162.7 (m, 4F, m-F). dB (96.3 MHz, C6D6): 6.2 (br).
The bis(pentafluorophenyl)boranes 3ae3d were isolated as the
SMe2 adducts following the general procedure presented below
for 3a$SMe2, while the pentafluorophenylboranes 4ae4d were

48
E.A. Jacobs et al. / Journal of Organometallic Chemistry 730 (2013) 44e48
4.1.4. (C6F5)B((CH2)5CH3)2 (4b)
was solved using XS [18] (incorporated in SHELXTL). Non-hydrogen
atoms were refined with anisotropic thermal parameters and
hydrogen atoms were placed in idealized positions and refined
using the riding model. No missed symmetry was reported by
PLATON [19]. The structure was refined (weighted least-squares
refinement on F2) and the final least-squares refinement converged
dH (300.1 MHz, C6D6): 1.1e1.7 (m, 20H, CH2), 0.9 (t, 3JH,H ¼ 6 Hz,
6H, CH3). dC (75.5 MHz, {1H}, C6D6): 33.3 (CH2), 32.6 (CH2), 31.8
(BCH2), 25.4 (CH2), 23.6 (CH2), 14.8 (CH3). dF (282.4 MHz,
3
C6D6): ꢀ134.0 (m, 2F, o-F), ꢀ153.5 (t, JF,F ¼ 20 Hz, 1F, p-F), ꢀ161.7
(m, 2F, m-F). dB (96.3 MHz, C6D6): 84.9 (br).
to R1 ¼ 0.0425 (I > 2
s
(I), 3145 data) and wR2 ¼ 0.1331 (F2, 3273
4.1.5. (C6F5)2B(CH2CH(C6H5)2)∙SMe2 (3c$SMe2)
data, 210 parameters, 2 restraints).
dH (300.1 MHz, C6D6): 6.8e7.3 (m, 10H, C6H5), 3.9 (t, 3JH,H ¼ 7 Hz,
3
1H, CH), 2.2 (d, JH,H ¼ 7 Hz, 2H, CH2), 0.9 (s, 6H, SMe2). dC
Acknowledgement
(75.5 MHz, {1H}, C6D6): 147.4 (Cipso), 128.3 (CH), 127.3 (CH), 125.8
(CH), 49.9 (CH), 27.4 (BCH2), 18.8 (SMe2). dF (282.4 MHz,
We thank the University of East Anglia for financial support. EJ is
the recipient of an A. R. Katritzky scholarship. The authors would
like to thank Dr. Anna-Marie Fuller for helpful discussions.
3
3
C6D6): ꢀ130.0 (d, JF,F ¼ 20 Hz, 4F, o-F), ꢀ156.1 (t, JF,F ¼ 21 Hz, 2F,
p-F), ꢀ162.8 (m, 4F, m-F). dB (96.3 MHz, C6D6): 1.6 (br).
4.1.6. (C6F5)B(CH2CH(C6H5)2)2 (4c)
dH (300.1 MHz, C6D6): 6.8e7.2 (m, 20H, C6H5), 4.2 (t, 3JH,H ¼ 8 Hz,
Appendix A. Supplementary material
3
2H, CH), 2.3 (d, JH,H ¼ 8 Hz, 4H, CH2). dC (75.5 MHz, {1H}, C6D6):
CCDC 885114 (5$SMe2) contains the crystallographic data for
this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
145.9 (Cipso), 128.5 (CH), 127.5 (CH), 126.2 (CH), 47.7 (CH), 38.5
(BCH2). dF (282.4 MHz, C6D6): ꢀ132.7 (m, 2F, o-F), ꢀ153.0 (t,
3JF,F ¼ 21 Hz, 1F, p-F), ꢀ162.0 (m, 2F, m-F). dB (96.3 MHz, C6D6): 83.4
(br).
References
4.1.7. (C6F5)2B(CHCH(SiMe3))∙SMe2 (3d$SMe2)
Formed a microcrystalline solid following removal of solvents.
Elemental analysis found (%): C, 44.98; H, 3.30. Calculated for
C19H17BF10SSi: C, 45.07; H, 3.38. dH (300.1 MHz, C6D6): 7.0 (dm,
3JH,H ¼ 21 Hz,1H, CH), 5.9 (d, 3JH,H ¼ 21 Hz,1H, CH), 2.1 (s, 6H, SMe2),
0.07 (s, 9H, SiMe3). dC (75.5 MHz, {1H}, C6D6): 145.8 (CH), 117.4
(BCH), 20.6 (SMe2), ꢀ1.2 (SiMe3). dF (282.4 MHz, C6D6): ꢀ130.9 (m,
[1] A.G. Massey, A.J. Park, F.G.A. Stone, Proc. Chem. Soc. 212 (1963).
[2] W.E. Piers, Adv. Organomet. Chem. 52 (2005) 1e76.
[3] K. Ishihara, H. Yamamoto, Eur. J. Org. Chem. (1999) 527e538.
[4] (a) E.Y.X. Chen, T.J. Marks, Chem. Rev. 100 (2000) 1391e1434;
(b) G. Erker, Dalton Trans. (2005) 1883e1890;
(c) M. Bochmann, Organometallics 29 (2010) 4711e4740.
[5] (a) J.L.W. Pohlmann, F.E. Brinckman, Naturforsch 20b (1965) 5e11;
(b) S. J. Lancaster, http://cssp.chemspider.com/Article.aspx?id¼215.
[6] D.J. Parks, R.E.v.H. Spence, W.E. Piers, Angew. Chem. Int. Ed. Engl. 34 (1995)
809e811.
3
4F, o-F), ꢀ157.2 (t, JF,F ¼ 20 Hz, 2F, p-F), ꢀ163.8 (m, 4F, m-F). dB
(96.3 MHz, C6D6): ꢀ0.5 (br).
[7] D.J. Parks, W.E. Piers, G.P. Yap, Organometallics 17 (1998) 5492e5503.
[8] D.J. Parks, W.E. Piers, Tetrahedron 54 (1998) 15469e15488.
[9] W.E. Piers, T. Chivers, Chem. Soc. Rev. 26 (1997) 345e354.
[10] M. Hoshi, K. Shirakawa, M. Okimoto, Tetr. Lett. 48 (2007) 8475e8478.
[11] See for example: (a) P. Spies, G. Kehr, K. Bergander, B. Wibbeling, R. Fröhlich,
G. Erker, Dalton Trans. (2009) 1534e1541;
4.1.8. (C6F5)B(CHCH(SiMe3))2 (4d)
dH (300.1 MHz, C6D6): 7.3 (m, 2H, CH), 6.2 (m, 2H, CH), 0.08 (s,
9H, SiMe3), 0.05 (s, 9H, SiMe3). dC (75.5 MHz, {1H}, C6D6): 168.6
(CH), 141.7 (BCH), 0.13 (SiMe3), ꢀ1.4 (SiMe3). dF (282.4 MHz,
3
(b) A.R. Cabrera, Y. Schneider, M. Valderrama, R. Fröhlich, G. Kehr, G. Erker,
R.S. Rohas, Organometallics 29 (2010) 6104e6110;
(c) B.H. Xu, G. Kehr, R. Fröhlich, S. Grimme, G. Erker, J. Am. Chem. Soc. 133
(2011) 3480e3491;
C6D6): ꢀ129.9 (m, 2F, o-F), ꢀ152.2 (t, JF,F ¼ 20 Hz, 1F, p-F), ꢀ161.9
(m, 2F, m-F). dB (96.3 MHz, C6D6): 63.5 (br).
(d) B.H. Xu, G. Kehr, R. Fröhlich, G. Erker, Organometallics 30 (2011)
5080e5083;
(e) S. Schwendemann, R. Fröhlich, G. Kehr, G. Erker, Chem. Sci. 2 (2011)
1842e1849;
4.2. Preparation of pentafluorophenyl-9-borobicyclo[3.3.1]
nonane$SMe2 (5$SMe2)
A sample of 2$SMe2 (1.04 g, 4.3 mmol) was dissolved in toluene
(75 ml). To this was added dropwise 1,5-cyclooctadiene (0.53 ml,
4.3 mmol) at room temperature. The mixture was heated to reflux
for 1 h. Once cooled, the toluene was removed to give a colorless oil.
X-ray quality crystals were obtained by dissolution in 1 ml of neat
dimethylsulfide and cooling. The conversion was quantitative by
11B NMR spectroscopic analysis and the product was isolated as
a colorless solid (1.18 g, 79%). Elemental analysis found (%): C, 54.81;
H, 5.67. Calculated for C16H20BF5S: C, 54.88; H, 5.76. 1H NMR (C6D6):
(f) J. Ugolott, G. Dierker, R. Fröhlich, G. Kehr, G. Erker, J. Organomet. Chem. 696
(2011) 1184e1188;
(g) E. Theuergarten, D. Schlüns, J. Grunenberg, C.G. Daniliuc, P.G. Jones,
M. Tamm, Chem. Commun. (2010) 8561e8563;
(h) A.M. Chapman, M.F. Haddow, J.P.H. Orton, D.F. Wass, Dalton Trans. (2010)
6184e6186;
(i) C.F. Jiang, O. Blacque, H. Berke, Organometallics 28 (2009) 5233e5239.
[12] A.M. Fuller, D.L. Hughes, S.J. Lancaster, C.M. White, Organometallics 29 (2010)
2194e2197.
[13] (a) E.F. Knights, H.C. Brown, J. Am. Chem. Soc. 90 (1968) 5280e5281;
(b) H.C. Brown, E.F. Knights, C.G. Scouten, J. Am. Chem. Soc. 96 (1974)
7765e7770.
[14] (a) H.C. Brown, S.U. Kulkarni, J. Org. Chem. 44 (1978) 2422e2425;
(b) H.C. Brown, J. Org. Chem. 46 (1981) 4599e4600.
[15] K. Essalah, J.-C. Barthelat, V. Montiel, S. Lachaize, B. Donnadieu, B. Chaudret,
S. Sabo-Etienne, J. Organomet. Chem. 680 (2003) 182e187.
[16] H. Braunschweig, G. D’Andola, T. Welton, A.J.P. White, Chem. Eur. J. 12 (2006)
600e606.
[17] Programs CrysAlisPro, Oxford Diffraction Ltd., Abingdon, UK, 2010.
[18] G.M. Sheldrick, Acta Cryst. A64 (2008) 112e122.
[19] (a) A.L. Spek, J. Appl. Cryst. 36 (2003) 7e13;
d
1.5e2.2 (14H, mm), 1.1 (6H, s). 19F NMR (C6D6):
d
ꢀ130.4 (2F, m, o-
F), ꢀ155.2 (1F, m, p-F), ꢀ162.9 (2F, m, m-F). 11B NMR (C6D6):
d C
19. 13
NMR (C6D6, partial): d 33.3 (CH2), 25.1 (CH2), 24.3 (CH), 17.3 (SMe2).
Crystals of 5$SMe2 were examined at 140 K on an Oxford
Diffraction Xcalibur-3/Sapphire3-CCD diffractometer, equipped
with Mo-K
were measured by thin-slice
using the CrysAlisPro-CCD and -RED programs [17]. The structure
a
radiation and graphite monochromator. Intensity data
u
- and 4-scans. Data were processed
(b) A.L. Spek, Acta Cryst. A46 (1990) C34.