for 10 min, and then injected into the MS at 20 mL minꢀ1. The
amounts correspond to a 1.25% catalyst loading (and 1.25% loading
of the charged ligand).
Notes and references
z Experimental details: all synthesis was performed under an inert
atmosphere of N2 using standard glovebox or Schlenk procedures.
Solvents were HPLC grade and purified on an MBraun solvent
purification system. All other chemicals were used as obtained
(Aldrich, Oakville, Canada). Gases were obtained from Airgas
(Calgary, Canada). NMR spectra were collected on either an
AV-300 or AV-360 Bruker spectrometer. Internal references to CHCl3
(1H d = 7.26 ppm) and external reference to 85% aqueous H3PO4
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(
31P) were used as appropriate. [NH4][1]18 (11.38 g, 31 mmol) was
dissolved in 100 mL warm deionised water, and bis(triphenyl-
phosphine)iminium chloride (17.34 g, 31 mmol) was dissolved in
60 mL dichloromethane. The two solutions were mixed together,
stirred vigorously for 5 min and transferred to a separating funnel.
30 mL of water containing ammonium chloride was added, the
mixture was shaken and allowed to settle. The lower organic layer
was collected, and the majority of the solvent was removed by rotary
evaporation. The resulting material was left under vacuum overnight
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1
to obtain the product as a white solid (24.21 g, 89% yield). H NMR
(300 MHz, CD2Cl2) d = 7.14–7.20 (m, 1 H), 7.22–7.32 (m, 10 H),
7.44–7.52 (m, 25 H), 7.62–7.68 (m, 6 H), 7.80–7.86 (m, 2 H). 31P NMR
(300 MHz, CD2Cl2)
d
=
ꢀ4.5 (s, PPh2C6H4SO3ꢀ), 21.6
(s, N(PPh3)2+). All the mass spectra and gas phase experiments were
performed on a Micromass Q-ToF micro hybrid quadrupole/time-
of-flight mass spectrometer in negative-ion mode using pneumatically-
assisted electrospray ionisation. Capillary voltage: 2900 V. Cone
voltage: 10 V. Extraction voltage: 0.5 V. Source temperature: 30 1C.
Desolvation temperature: 60 1C. Cone gas flow: 100 L hꢀ1. Desolvation
gas flow: 200 L hꢀ1. Collision voltage: 2 V (for MS experiments).
Collision voltage: 15 V (for MS/MS experiments). Collision pressure:
2.05 ꢃ 0.05 ꢂ 10ꢀ5 mbar. Low and high mass resolution: 10.0. MCP
voltage: 2700 V. Solutions were run in dichloromethane and
introduced to the mass spectrometer by a syringe pump at a rate of
20 mL minꢀ1. MS/MS experiments were conducted with argon in the
collision cell. The appropriate peak was mass selected (usually with a
broad enough window to accommodate the full isotope pattern,
i.e. B8 m/z) and the selected ion fragmented at the stated voltage(s)
in the argon-filled collision cell. All mass spectra were collected for a
sufficiently long period to obtain a signal-to-noise ratio of at least
20 : 1; this ranged from a few seconds for ordinary mass spectra to
10 minutes for some of the MS/MS experiments. For each experiment,
palladium tetrakistriphenylphosphine (0.006 g, 5 mmol) and 1 (0.004 g,
5 mmol) were dissolved in 5 mL dichloromethane. For reductive
elimination experiments, the catalyst solution was then mixed with
the appropriate para-substituted aryl iodide (0.4 mmol), and phenyl-
acetylene (0.044 mL, 0.4 mmol) and triethylamine (0.055 mL,
0.4 mmol) were added. The reaction mixture was allowed to stand
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c
7414 Chem. Commun., 2010, 46, 7412–7414
This journal is The Royal Society of Chemistry 2010