Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
Photoinduced alkyl group exchange of ethylzinc alkoxides: X-ray crystal
structure of iodomethylzinc methoxide**
André B. Charette,* André Beauchemin, Sébastien Francoeur, Francine Bélanger-Gariépy, and
Gary D. Enright
Supplementary Information
Experimental Section
Dichloromethane-d2 (~ 0.7 mL) and 1,2-dimethoxyethane (0.036 mL, 0.35 mmol) were added in
a previously purged NMR tube, under argon. The tube was capped with a septum and secured with
Teflon® tape. Diethylzinc (0.036 mL, 0.35 mmol) and methanol (0.0142 mL, 0.35 mmol) were then
added at room temperature and gas evolution was observed. The tube was shook twice and
diiodomethane (0.026 mL, 0.35 mmol) was added after at least 5 minutes. The tube was shook
twice and the colorless solution was irradiated at room temperature using a 300 W sunlamp
(OSRAM, Ultra-Vitalux). The lamp was placed at a distance of 20 cm from the NMR tube in order
to avoid sample warming and loss of solvent. The solution was irradiated for 45 minutes and then
analyzed by NMR, showing complete conversion and the presence of different aggregates in
solution. 1H NMR (400 MHz, CD2Cl2)  3.92 (s, 3H), 3.91 (s, 3H), 3.88 (s, 3H), 3.85 (s, 3H), 1.50
(s, 2H), 1.48 (s, 2H), 1.47 (s, 2H), 1.36 (s, 2H); 13C NMR (100 MHz, CD2Cl2)  57.9, 56.8, –20.6, –
31.4, –32.8. Colorless crystals generally deposited within 3 hours. Once the crystals were deposited,
the NMR tube was kept at –78 ˚C while waiting for X-ray analysis.
Iodomethylzinc methoxyde (NMR in solution)
Et2 Zn + MeOH
DME,
CD2 Cl2
A
B
C
EtZnOMe•DME
D
CH2I2,
h
E
F
MeOZnCH2I•DME + Et-I
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
C
C
D
F
F
B
E A
A
A
C
C
F
B
F
E
Figure 1. 1H NMR before and after irradiation of the solution
Iodomethylzinc methoxyde (NMR in the solid-state)
Et2 Zn + MeOH
DME (2 équiv.),
CH2 Cl2
MeOZnEt•DME
CH2I2,
h
A
"MeOZnCH2 I"
The procedure described in the experimental section was repeated, using dichloromethane (1.0
mL), 1,2-dimethoxyethane (0.104 mL, 1.00 mmol), diethylzinc (0.0512 mL, 0.50 mmol), methanol
(0.0203 mL, 0.50 mmol) and diiodomethane (0.0403 mL, 0.50 mmol). The solution was irradiated 1
hour with a 300 W sunlamp (OSRAM, Ultra-Vitalux) and routinely crystals deposited before the
end of the irration. This procedure was repeated 11 times on the same scale to afford colorless
crystals (suitable for X-ray analysis) in 9 cases. After introduction of the samples in the glove-box,
the crystals were then combined, solvent was removed and the solid was grind to a fine powder
(~0.6 g). The solid was dried under a nitrogen stream and inserted into the sample holder.
MAS NMR (75 MHz)  62, 56, –24 (s, broad).
13C
CP-
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
A
Figure 2. 13C CP-MAS NMR of (MeO)8Zn7(CH2I)6
Et2Zn + HOCH2 CH2OH
DME
CH2 I2
EtZnOCH2 CH2OZnEt
CD2 Cl2
ICH2ZnOCH2CH 2OZnCH2I
h
Dichloromethane-d2 (~0.7 mL) and 1,2-dimethoxyethane (0.036 mL, 0.35 mmol) were
added in a previously purged NMR tube, under argon. The tube was capped with a septum and
secured with Teflon tape. Diethylzinc (0.036 mL, 0.35 mmol) and ethylene glycol (0.010 mL,
0.18 mmol) were then added at room temperature and gas evolution was observed. The tube was
shook twice and diiodomethane (0.028 mL, 0.35 mmol) was added after at least 5 minutes. The tube
was shook twice and then irradiated at room temperature using a 300 W sunlamp (OSRAM, UltraVitalux). The lamp was placed at a distance of 20 cm from the NMR tube in order to avoid sample
warming and loss of solvent. The solution was irradiated for 60 minutes. Benzene (0.031 mL, 0.35
mmol) was then added as an internal standard and the solution was analyzed by NMR. Complete
disappearance of the CH2I2 and formation of 2 equivalents of ethyl iodide (using the benzene peak
as an internal standard) were observed.
Et2Zn + HOCH2 CH2OH
DME
CD2 Cl2
CH2 I2
EtZnOCH2 CH2OZnEt
[-CH2ZnOCH2CH2 OZn-]x
h
Dichloromethane-d2 (~0.7 mL) and 1,2-dimethoxyethane (0.036 mL, 0.35 mmol) were
added in a previously purged NMR tube, under argon. The tube was capped with a septum and
secured with Teflon tape. Diethylzinc (0.036 mL, 0.35 mmol) and ethylene glycol (0.010 mL,
0.18 mmol) were then added at room temperature and gas evolution was observed. The tube was
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
shook twice and diiodomethane (0.014 mL, 0.18 mmol) was added after at least 5 minutes. The tube
was shook twice and then irradiated at room temperature using a 300 W sunlamp (OSRAM, UltraVitalux). The lamp was placed at a distance of 20 cm from the NMR tube in order to avoid sample
warming and loss of solvent. The solution was irradiated for 60 minutes. Benzene (0.031 mL, 0.35
mmol) was then added as an internal standard and the solution was analyzed by NMR. Complete
disappearance of the CH2I2 and formation of 2 equivalents of ethyl iodide (using the benzene peak
as an internal standard) were observed.