Dalton Transactions
Paper
(br); HRMS (EI): m/z [M]+ calcd for C28H29NO2P2+: 473.1674, nonane as the internal standard. The individual oligomeriza-
found: 473.1673; Anal. Calcd for C28H29NO2P2 (%): C, 71.03; tion products were identified by GC-MS. The remainder of the
H, 6.17; N, 2.96; found: C, 70.50; H, 6.38; N, 2.83.
upper-layer solution was filtered to isolate the solid polymeric
Synthesis of ligand L4, 1-(2-chlorophenoxy)-N-(diphenylphos- products. The solid products were suspended in 10% aq.
phino)-N-isopropyl-1-phenylphosphinamine. L4 has been pre- HCl and stirred for 24 h, dried under reduced pressure and
pared similarly to L1 with a yield of 55.4%, starting from weighed.
2-chlorophenol (625.9 mg, 3.9 mmol), sodium hydride (60%
dispersion in paraffin), (155.6 mg, 3.9 mmol) and Ph2PN(Pri)-
PPh(Cl) (1.87 g, 4.9 mmol). 1H NMR (400 MHz, CDCl3) δ =
7.67–7.64(m, 2H), 7.49–7.42 (m, 5H), 7.39–7.37 (m, 2H),
Acknowledgements
7.35–7.28 (m, 4H), 7.17–7.08 (m, 3H), 7.01–6.96 (m, 1H), Financial support from the Shanghai Pujiang Talent Program
6.90–6.88 (m, 1H), 6.76 (d, J = 8.1 Hz, 1H), 3.92–3.86 (m, 1H), (11PJ1402500), the Fundamental Research Funds for the
1.43 (d, J = 6.5 Hz, 3H), 1.01 (d, J = 6.6 Hz, 3H); 13C NMR Central Universities (WK1114014), and the National Natural
(100 MHz, CDCl3) δ = 152.34, 152.21, 140.65, 140.63, 140.47, Science Foundation of China (21171056, u1162111 and
140.52, 139.59, 139.49, 139.46, 139.36, 133.87, 133.84, 133.64, u1362111) is greatly acknowledged.
133.60, 132.19, 131.99, 130.19, 130.13, 129.99, 129.38, 129.31,
129.08, 128.42, 128.35, 128.25, 128.20, 128.11, 128.06, 128.00,
127.54, 124.68, 124.29, 124.28, 124.44, 119.23, 119.02, 50.49,
Notes and references
50.27, 24.51, 24.48, 24.39, 24.37, 24.13, 24.01; 31P NMR
(162 MHz, CDCl3) δ = 128.37 (d, J = 22.4 Hz), 39.29 (br); HRMS
1 (a) D. S. McGuinness, Chem. Rev., 2011, 111, 2321;
(b) J. T. Dixon, M. J. Green, F. M. Hess and D. H. Morgan,
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(EI): m/z [M]+ calcd for C27H26ClNOP2 : 477.1178, found:
+
477.1176; Anal. Calcd for C27H26ClNOP2 (%): C, 67.86; H, 5.48;
N, 2.93; found: C, 67.50; H, 5.78; N, 2.62.
Synthesis of ligand L5, N-cyclohexyl-N-(diphenylphosphino)-
1-phenoxy-1-phenylphosphinamine. L5 has been prepared
similarly to L1 with a yield of 47.4%, starting from phenol
(132.9 mg, 1.4 mmol), sodium hydride (60% dispersion in
paraffin), (56.8 mg,1.4 mmol) and Ph2PN(Cy)PPh(Cl)
(753.97 mg, 1.8 mmol). 1H NMR (400 MHz, CDCl3) δ =
7.49–7.48 (m, 2H), 7.32 (m, 2H), 7.26–7.21 (m, 8H), 7.15–7.09
(m, 2H), 7.09–7.04 (m, 1H), 7.01–6.97 (m, 2H), 6.90–6.84 (m,
3H), 3.28–3.21 (m, 1H), 1.75–1.57 (m, 4H), 1.46–1.36 (m, 2H),
1.18–1.14 (m, 1H), 0.99–0.88 (m, 1H), 0.85–0.83 (m, 1H),
0.79–0.74 (m, 1H); 13C NMR (100 MHz, CDCl3) δ = 155.55,
155.43, 140.76, 140.72, 140.61, 140.57, 139.19, 139.03, 138.69,
138.62, 138.55, 138.16, 132.68, 132.65, 132.45, 132.43, 131.05,
130.85, 128.99, 128.79, 128.31, 128.13, 127.95, 127.21, 127.14,
126.99, 126.93, 126.89, 126.85, 121.11, 121.09, 118.23, 118.13,
57.21, 57.08, 25.19, 25.04, 24.34, 24.24; 31P NMR (162 MHz,
CDCl3) δ = 128.00 (d, J = 21.1 Hz), 43.10 (br); HRMS (EI): m/z
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[M]+ calcd for C30H31NOP2 : 483.1881, found: 483.1880; Anal.
+
Calcd for C30H31NOP2 (%): C, 74.52; H, 6.46; N, 2.90; found:
C, 74.33; H, 6.63; N, 2.69.
Oligomerization of ethylene
A 120 mL stainless steel reactor was dried at 120 °C for 3 h
under vacuum, and then cooled down to the desired reaction
temperature. The precatalysts and co-catalysts were combined
in a Schlenk vessel in the ratios indicated in Tables 1–3. The
resulting mixture was stirred for 1 min and immediately trans-
ferred to the reactor. Then the reactor was immediately pres-
surized. After the specified reaction time, the reaction was
stopped by shutting in the ethylene feed, cooling the system at
0 °C, depressurizing, and quenched by the addition of 30 mL
of 10% aq. HCl. A small sample of the upper-layer solution
was filtered through a layer of Celite and analysed by GC using
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Dalton Trans.