Dalton Transactions
Paper
Synthesis of 1-PdBF4
Notes and references
In a N2-filled glovebox,
a solution of NOBF4 (0.009 g,
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0.072 mmol) in MeCN (1 mL) was added to a suspension of
1-PdI (0.100 g) in MeCN (5 mL) in a 20 mL scintillation vial.
The vial was sealed and left gently stirring at room temperature
for 12 h. The reaction mixture was centrifuged, and the orange
supernatant was decanted. A fresh solution of NOBF4 (0.009 g,
0.072 mmol) in MeCN (6 mL) was added and the reaction
again stirred at room temperature for 12 h. The solid was col-
lected by centrifugation, washed with MeCN (3 × 5 mL), and
dried briefly in vacuo. 1-PdBF4 was isolated as an off-white
microcrystalline powder (0.100 g). 31P{1H} NMR (162.0 MHz,
3/1 v/v CF3COOH/C6D6): δ 76.2 (s); 75.2 (s); 74.5 (s); 70.2 (s).
Anal. calcd for chemical formula: [Zr6O4(OH)4(OAc)2.4{(PNNNP)
Pd(MeCN)}2.4(BF4)2.4 (C88.8H68.8N9.6O12.8B2.4F9.6Zr6Pd2.4)]: C,
34.21; H, 2.30; N, 4.31. Found: C, 31.81; H, 2.00; N, 4.10;
I, <0.25.
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General procedure for catalytic hydroamination reactions with
2 and 4
In a N2-filled glovebox, a vial was charged with 2 or 4
(0.1 mmol), 5 mol% catalyst, 1,4-dioxane (0.5 mL), C6D6
(0.1 mL), and
(0.005–0.01 mmol) as an internal standard. The reaction
a known amount of hexamethylbenzene
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mixture was transferred to an NMR tube and heated at 95 °C
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1
for 4 h. The product yields were determined by H NMR spec-
1
troscopy for 2 (Fig. S11–S17, ESI†) and H NMR spectroscopy
or GC-FID for 4 (Fig. S19–S22, ESI†). For recycling experiments,
1-PdBF4 was isolated from the reaction mixture via centrifu-
gation, washed with 1,4-dioxane (3 × 2 mL), and resubjected to
the reaction conditions described above.
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General procedure for carbonyl–ene reactions
In a N2-filled glovebox, a 1 dram screw-top vial fitted with a
Teflon lined cap was charged with 8 (0.05 mmol), 10 mol%
catalyst, toluene (2 mL), and a known amount of hexamethyl
benzene (0.01–0.04 mmol) as an internal standard. The reac-
tion mixture was heated at 100 °C for 30 minutes. The product
yields were determined by GC-FID. For recycling experiments,
1-PdBF4 was isolated from the reaction mixture via centrifu-
gation, washed with toluene (3 × 2 mL), and resubjected to the
reaction conditions described above.
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Conflicts of interest
There are no conflicts to declare.
22 S. Ahn, S. L. Nauert, C. T. Buru, M. Rimoldi, H. Choi,
N. M. Schweitzer, J. T. Hupp, O. K. Farha and
J. M. Notestein, J. Am. Chem. Soc., 2018, 140, 8535–8543.
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Acknowledgements
Acknowledgment is made to the Donors of the American 24 S. A. Burgess, A. Kassie, S. A. Baranowski, K. J. Fritzsching,
Chemical Society Petroleum Research Fund (Grant
55281-DNI-3) for support of this research.
K. Schmidt-Rohr, C. M. Brown and C. R. Wade,
J. Am. Chem. Soc., 2016, 138, 1780–1783.
This journal is © The Royal Society of Chemistry 2018
Dalton Trans.