Diphenylsilylene

Article abstract of DOI:10.1021/ja0653223

Lamp or pulsed laser photolysis of 1,1,3,3-tetramethyl-2,2-diphenyl-1,2,3-trisilacycloheptane affords diphenylsilylene (SiPh₂) with significantly higher selectivity than that reported previously from other SiPh₂ precursors, allowing

Full text of DOI:10.1021/ja0653223

Published on Web 10/20/2006
Diphenylsilylene
Andrey G. Moiseev and William J. Leigh*
Department of Chemistry, McMaster UniVersity, 1280 Main Street West, Hamilton, Ontario, Canada L8S 4M1
Received July 25, 2006; E-mail: leigh@mcmaster.ca
In spite of great interest over the past 30 years in the chemistry
of silylenes,1 the silicon analogues of singlet carbenes, few
quantitative data exist on the reactivity of simple transient deriva-
tives in solution. Dimethylsilylene (SiMe2) has been studied by Das
and Shizuka and co-workers,2,3 who measured rate constants for a
number of representative reactions in solution by flash photolysis
methods, and a similar study of dimesitylsilylene (SiMes2) has been
reported by Conlin and co-workers.4 Similar studies of methylphe-
A competitive trapping experiment was carried out, in which a
0.02 M solution of 3 in C6D12 containing MeOH (0.09 M) and
nyl- (SiMePh)5 and diphenylsilylene (SiPh2)6 had been reported
somewhat earlier, but the reported rate constants are so significantly
triethylsilane (Et3SiH; 0.25 M) was photolyzed to ca. 50% conver-
different from those reported later for SiMe2 and SiMes2 with
sion, monitoring by NMR spectroscopy throughout the photolysis.
Three products were formed: 4, 5, and 1,1,1-triethyl-2,2-diphenyl-
disilane (6), which was identified in a separate experiment in which
3 was photolyzed in C6D12 containing only Et3SiH (eq 2).
similar substrates that it was soon recognized that misassignments
must have been made.1a Indeed, the time-resolved UV/vis spectra
assigned to SiMePh and SiPh2 in these reports (λmax 440-445 nm)5,6
differ markedly from those measured in hydrocarbon glasses at 77
K from the same precursors (λmax 490-495 nm).7 All of the
arylsilylenes that were studied in these early efforts, both in solution
and frozen matrixes, were generated by photolysis of acyclic
Compounds 4 and 6 were formed in relative yields of 4/6 ) 1.59
( 0.03, which yields a rate constant ratio of kMeOH/kEt SiH ) 4.4 (
3
0.2 for the reaction of SiPh2 with the two substrates.
Laser flash photolysis of flowing, deoxygenated solutions of 3
(∼0.09 mM) in anhydrous hexane gave rise to three distinct
trisilanes, which are known to extrude the central SiRR′ group as
the major photoreaction. Phenylated systems are known also to
transient species with overlapping absorption spectra centered in
afford conjugated silene derivatives, formed by 1,3-silyl migration
the 460-520 nm range. Two of these are formed with the laser
pulse: a long-lived species (τ > 100 µs) with λmax ) 460 nm and
a shorter-lived one (τ ≈ 1 µs) with λmax ≈ 520 nm. A third species,
into the ortho position of one of the phenyl rings.8 In the case of
trisilane 1, the compound employed for the generation of SiPh2,
this process (yielding 2) occurs in solution with similar efficiency
which also exhibits λmax ≈ 460 nm and τ ≈ 10 µs, was observed
to SiPh2 extrusion (eq 1).9 Our own experience with silenes of this
to grow in over the first 1 µs after excitation. Both the lifetime of
the 520 nm transient and the peak intensity of the short-lived 460
nm species showed exquisite sensitivity to adventitious water or
intentionally added reagents. For example, the addition of 0.6 mM
type10 suggested that this might be the source of the complications
encountered in early time-resolved studies of 1 and similar
derivatives.
Et3SiH reduced the lifetime of the 520 nm transient to τ ≈ 370 ns
and the peak intensity of the 460 nm signal by ca. 25%, compared
to their values in the absence of silane. The lifetime of the long-
lived 460 nm species was unaffected under these conditions. Time-
resolved UV/vis spectra recorded 64-80 ns and 1.5-1.6 µs after
excitation in the presence of 0.6 mM Et3SiH are shown in Figure
Silylene extrusion also occurs in high yield from cyclic trisi-
lanes.11 This led us to wonder whether an appropriately substituted
cyclic analogue of 1 might be a significantly cleaner source of SiPh2
for study by flash photolysis methods, as the isomeric cyclic silene
that would be formed by [1,3]-silyl migration might be expected
to suffer from sufficient strain that its formation might be suppressed
relative to silylene extrusion.
1, along with the isolated spectrum of the 520 nm species, calculated
by subtracting the late spectrum from the early one. The figure
also shows the spectrum of a photolyzed solution of 3 in a
3-methylpentane (MP) glass at 78 K. The latter spectrum is nearly
identical to that obtained from trisilane 1 under the same conditions,
exhibiting a long wavelength absorption centered at λmax ) 505
nm, in reasonable agreement with the spectrum originally reported
for 1 under similar conditions, and assigned to SiPh2.7
The short-lived species is best monitored at 530 nm, where its
absorptions are better separated from those due to the longer-lived
transient products. Addition of small amounts of MeOH, Et3SiH,
isoprene, 4,4-dimethyl-1-pentene, or tert-butylacetylene12 led to
acceleration of the first-order decay of the species in direct
proportion to their concentrations, resulting in linear plots of the
decay rate constant (kdecay) versus concentration in every case. The
slopes of the plots are the absolute second-order rate constants for
reaction, and are listed in Table 1. Also listed for comparison are
the reported values for reaction of SiMe22,3 and of the germanium
Indeed, steady-state photolysis (254 nm) of a C6D12 solution of
cyclic trisilane 3 (0.05 M) and methanol (MeOH; 0.16 M) led to
the formation of diphenylmethoxysilane (4, 69%), disilane 5 (83%),
1
and five minor products in 14% combined yield (eq 2), whose H
NMR and mass spectra are consistent with adducts of MeOH and
an isomer of 3. The quantum yield for consumption of 3 was
determined to be Φ-3 ) 0.54 ( 0.09. These results confirm that
SiPh2, which is trapped by MeOH as 4, is formed in significantly
higher yield from 3 than from the acyclic parent (1),9b and with
high enough efficiency that its direct detection and characterization
by flash photolysis methods should be possible.
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10.1021/ja0653223 CCC: $33.50 © 2006 American Chemical Society

C O M M U N I C A T I O N S
products of these reactions. The latter is evident from the fact that
GePh2 reacts reversibly with MeOH, the alkene, and the diene on
the microsecond time scale,13,14 while SiPh2 appears to react
irreversibly. The trends are similar to those exhibited by the
methylated counterparts, SiMe2 and GeMe2, under similar condi-
tions.16
The insensitivity of the lifetime of the long-lived 460 nm species
to added Et3SiH was mirrored in the experiments with the other
scavengers studied. This is the behavior expected10 of a silene
intermediate analogous to that formed in the photolysis of 1.9 As
discussed above, minor products consistent with addition of MeOH
to such a species were observed in the steady-state experiments,
though they have not yet been isolated owing to their very low
individual yields. More complete identification of the minor
transient products of photolysis of 3 and analogous studies of the
transient photoproducts from 1 will be reported in due course, as
will the results of further studies of the reactivities of simple
transient silylenes in solution.
Figure 1. Transient absorption spectra recorded 64-80 ns (-O-) and 1.5-
1.6 µs (-0-) after the laser pulse, from laser flash photolysis of a 0.09 mM
solution of 3 in deoxygenated, anhydrous hexane containing 0.6 mM Et3-
SiH. Also shown is the difference spectrum (-b-; 80 ns minus 1.6 µs) and
the spectrum obtained after 254 nm photolysis of 3 in a MP glass at 78 K
(---). The inset shows transient decays recorded at 460 and 530 nm.
Acknowledgment. We thank the Natural Sciences and Engi-
neering Research Council of Canada for financial support and Ms.
Stephanie Ladowski for low-temperature UV/vis spectra.
Table 1. Absolute Rate Constants (kQ/109 M-1s-1) for Reaction of
SiPh2, SiMe2, and GePh2 with Selected Scavengers in
Hydrocarbon Solvents at 25 °C
Supporting Information Available: Synthesis and characterization
of compounds; detailed descriptions of product studies; flash photolysis
experiments; TD-DFT calculations. This material is available free of
charge via the Internet at http://pubs.acs.org.
1
kQ/109 M-1s-
a
b
c
scavenger (Q)
SiPh2
SiMe2
GePh2
MeOH
Et3SiH
isoprene
4,4-dimethyl-1-pentene
tert-butylacetylene
13.2 ( 0.3
2.8 ( 0.1
11.8 ( 1.0
8.7 ( 0.4
9.7 ( 0.4
9.1
3.6
9.4
7.3
8.0
6.1d
0.0006
5.5 d
4.2 d
5.2
References
(1) (a) Gaspar, P. P.; West, R. Silylenes. In The Chemistry of Organic Silicon
Compounds; Rappoport, Z., Apeloig, Y., Eds.; John Wiley & Sons: New
York, 1998; Vol. 2, pp 2463-2568. (b) Tokitoh, N.; Okazaki, R. Coord.
Chem. ReV. 2000, 210, 25 and references cited therein. (c) Tokitoh, N.;
Ando, W. In ReactiVe Intermediate Chemistry; Moss, R. A., Platz, M. S.,
Jones, M., Jr., Eds.; Wiley-Interscience: New York, 2004; pp 651-715.
(2) (a) Levin, G.; Das, P. K.; Lee, C. L. Organometallics 1988, 7, 1231. (b)
Levin, G.; Das, P. K.; Bilgrien, C.; Lee, C. L. Organometallics 1989, 8,
1206.
(3) (a) Shizuka, H.; Tanaka, H.; Tonokura, K.; Murata, K.; Hiratsuka, H.;
Ohshita, J.; Ishikawa, M. Chem. Phys. Lett. 1988, 143, 225. (b) Yamaji,
M.; Hamanishi, K.; Takahashi, T.; Shizuka, H. J. Photochem. Photobiol.,
A 1994, 81, 1.
a From plots of the pseudo-first-order rate constants (kdecay) for decay of
SiPh2 in hexane, monitored at 530 nm, versus scavenger concentration; errors
are reported as ( 2σ. b Data from refs 2, 3 (cyclohexane, 22 °C); diene )
2,5-dimethyl-1,3-hexadiene; alkene ) 1-hexene; alkyne ) trimethylsily-
lacetylene. c Data from refs 13, 14. d Reversible, with equilibrium constants
in the range 2000-6000 M-1 in hexane at 25 °C (see refs 13, 14).
homologue, GePh2,13,14 with the same or similar substrates. The
close correspondence between the rate constants for reaction of the
520 nm species from 3 and of SiMe2 with corresponding substrates
provides strong support for a silylene assignment. Further support
is provided by the excellent agreement between the absolute rate
constant ratio for reaction of the species with MeOH and Et3SiH
(4) Conlin, R. T.; Netto-Ferreira, J. C.; Zhang, S.; Scaiano, J. C. Organo-
metallics 1990, 9, 1332.
(5) (a) Gaspar, P. P.; Boo, B. H.; Chari, S.; Ghosh, A. K.; Holten, D.; Kirmaier,
C.; Konieczny, S. Chem. Phys. Lett. 1984, 105, 153. (b) Gaspar, P. P.;
Holten, D.; Konieczny, S.; Corey, J. Y. Acc. Chem. Res. 1987, 20, 329.
(6) Konieczny, S.; Jacobs, S. J.; Braddock Wilking, J. K.; Gaspar, P. P. J.
Organomet. Chem. 1988, 341, C17.
(7) Michalczyk, M. J.; Fink, M. J.; De Young, D. J.; Carlson, C. W.; Welsh,
K. M.; West, R.; Michl, J. Silicon, Germanium, Tin, Lead Compd. 1986,
9, 75.
(8) (a) Ishikawa, M.; Nakagawa, K.-I.; Ishiguro, M.; Ohi, F.; Kumada, M. J.
Organomet. Chem. 1978, 152, 155. (b) Ishikawa, M.; Nakagawa, K.-I.;
Enokida, R.; Kumada, M. J. Organomet. Chem. 1980, 201, 151.
(9) (a) Kira, M.; Miyazawa, T.; Koshihara, S.; Segawa, Y.; Sakurai, H. Chem.
Lett. 1995, 3. (b) Miyazawa, T.; Koshihara, S. Y.; Liu, C.; Sakurai, H.;
Kira, M. J. Am. Chem. Soc. 1999, 121, 3651.
(10) (a) Sluggett, G. W.; Leigh, W. J. J. Am. Chem. Soc. 1992, 114, 1195. (b)
Leigh, W. J.; Sluggett, G. W. Organometallics 1994, 13, 269.
(11) (a) Sakurai, H.; Kobayashi, Y.; Nakadaira, Y. J. Am. Chem. Soc. 1971,
93, 5272. (b) Sakurai, H.; Kobayashi, Y.; Nakadaira, Y. J. Am. Chem.
Soc. 1974, 96, 2656. (c) Bortwick, I.; Baldwin, L. C.; Sulkes, M.; Fink,
M. Organometallics 2000, 19, 139.
(kMeOH/kEt SiH ) 4.7 ( 0.3) and the value determined above by
3
competitive steady-state trapping.
Each of these reagents also quenched the formation of the short-
lived 460 nm transient completely, suggesting it is a product of
reaction of SiPh2 that is eliminated in the presence of silylene
scavengers. A likely candidate is the dimerization product, tetra-
phenyldisilene (Si2Ph4); its spectrum can be compared to that of
tetraphenyldigermene (Ge2Ph4; λmax ) 440 nm), which is similarly
formed from GePh2 under the same conditions and similarly
quenched in the presence of added scavengers.13,15 Time-dependent
DFT calculations (see Supporting Information) reproduce the red-
shifts in the absorption maxima of SiPh2 and Si2Ph4 relative to those
of the corresponding germanium analogues13 and yield values of
(12) Product studies of the reactions of SiPh2 with alkenes and dienes have
been reported by Tortorelli, V. J.; Jones, M., Jr.; Wu, S.; Li, Z.
Organometallics 1983, 2, 759.
(13) Leigh, W. J.; Harrington, C. R. J. Am. Chem. Soc. 2005, 127, 5084.
(14) Leigh, W. J.; Lollmahomed, F.; Harrington, C. R.; McDonald, J. M.
Organometallics 2006, 125, 5424.
λmax (equal to 565 and 486 nm for SiPh2 and Si2Ph4, respectively)
that are in acceptable agreement with the experimental spectra.
SiPh2 and GePh2 exhibit the same large differences in reactivity
toward Si-H insertion as do the parent (MH2) and dimethyl (MMe2)
metallylene analogues.16,17 The kinetic differences are much less
pronounced in the reactions with C-C multiple bonds and MeOH,
despite substantial differences in the stabilities of the primary
(15) Leigh, W. J.; Harrington, C. R.; Vargas-Baca, I. J. Am. Chem. Soc. 2004,
126, 16105.
(16) Leigh, W. J.; Lollmahomed, F.; Harrington, C. R. Organometallics 2006,
25, 2055.
(17) Boganov, S. E.; Egorov, M. P.; Faustov, V. I.; Krylova, I. V.; Nefedov,
O. M.; Becerra, R.; Walsh, R. Russ. Chem. Bull. 2005, 54, 483.
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