THE REACTION OF SILYLENES WITH AMINES
3
activated alumina under nitrogen using a Solv-Tek solvent
purification system (Solv-Tek, Inc).
Methoxydiphenylsilane (9),[36] 1H NMR, d 7.54 (dd, J=1.38,
2J=7.86), 7.25 (m, 6H), 5.36 (s, 1H), 3.52 (s, 3H), 29Si NMR d 9.7
(1JSi–H=212Hz).
Theoretical calculations were carried out using the GAUSSIAN09
Laser flash photolysis experiments
suite of programs.[56]
Laser flash photolysis experiments were carried out using a
Lambda Physik Compex 120 excimer laser filled with F2/Kr/Ne
(248nm, 20ns, 98–110mJ/pulse) and a Luzchem Research
mLFP-111 laser flash photolysis system, modified as described
previously.[55] The solutions were prepared in deoxygenated an-
hydrous hexanes such that the absorbance at 248nm was be-
tween 0.4 and 0.7. The solutions were flowed rapidly through a
7ꢁ7mm Suprasil flow cell connected to a calibrated 100mL or
250mL reservoir, which contained a glass frit to allow bubbling
of argon gas through the solution for 40min prior to and
throughout the experiment. The flow cell was connected to a
MasterflexTM 77390 peristaltic pump fitted with Teflon tubing
(Cole-Parmer Instrument Co.), which pulled the solution through
the cell at a constant rate of 2–3mL/min. The glassware, sample
cell, and transfer lines were dried in a vacuum oven (65–85ꢀC)
before use. Solution temperatures were measured with a
Teflon-coated copper/constantan thermocouple inserted into
the thermostatted sample compartment in close proximity to
the sample cell. Substrates were added directly to the reservoir
by a microliter syringe as aliquots of standard solutions.
Transient absorbance–time profiles were recorded by signal-
averaging of data obtained from 10–40 individual laser shots,
using neutral density filters as necessary to reduce the laser
intensity to achieve first order decay kinetics. Decay rate con-
stants were calculated by nonlinear least squares analysis of
the transient absorbance–time profiles using the PRISM 5.0 soft-
ware package (GraphPad Software, Inc.) and the appropriate
user-defined fitting equations, after importing the raw data from
the LUZCHEM mLFP software. Rate constants were calculated by
linear least-squares analysis of decay rate-concentration data
that spanned as large a range in transient decay rate as possible.
Errors are quoted as twice the standard error obtained from the
least-squares analyses.
Acknowledgement
We wish to thank the Natural Sciences and Engineering Research
Council of Canada for financial support, and congratulate
Professor Bob Moss on the occasion of his 70th birthday.
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1
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3
Tetraphenyldisiloxane (8),[45,46] 1H NMR, d 7.47 (d, J=7.56
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N,N-diethyl-1,1-diphenylsilanamine (6),[44] 1H NMR, d 7.53
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3
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J. Phys. Org. Chem. 2011, 24 937–946
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