Paper
Dalton Transactions
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ArH), 6.85 (t, JH,H = 7.4 Hz, 1 H, 4-ArH), 6.73–6.70 (m, 1 H, 3- colourless powder (5.5 g, 14.3 mmol, 49%). 1H NMR
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ArH), 2.96 (dd, JH,P = 4.5 Hz, 2JH,H = 13.7 Hz, 1 H, PCH2), 2.78 (600 MHz, THF-d8): δ [ppm] = 7.44 (t, JH,H = 7.5 Hz, 4 H,
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2
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(dd, JH,P = 4.1 Hz, JH,H = 12.7 Hz, 1 H, PCH2), 2.62 (t, JH,H
=
o-Ph), 7.28 (m, 4 H, m-Ph), 7.26 (m, 2 H, p-Ph), 2.66 (dm, JH,H
=
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13.7 Hz, 1 H, PCH2), 2.62 (t, JH,H = 12.7 Hz, 1 H, PCH2), 0.43 17.9 Hz, 4 H, NCH2), 2.16 (d, JH,P = 6.9 Hz, 2 H, PCH2), 1.48
(s, 9 H, SiMe3), −0.01 (s, 9 H, SiMe3); 13C{1H} NMR (151 MHz, (m, 1 H, CH) 1.02 (s, 18 H, CMe3); 13C{1H} NMR (151 MHz,
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C6D6): δ [ppm] = 146.1 (d, JC,P = 3.7 Hz, 1-ArC), 139.0 (d, JC,P THF-d8): δ [ppm] = 140.8 (d, JC,P = 14.6 Hz, ipso-Ph), 134.9 (d,
= 9.9 Hz, 1-ArC), 135.3 (s, 2-ArC), 134.4 (d, JC,P = 3.3 Hz, 6- 2JC,P = 13.2 Hz, m-Ph), 133.5 (d, 2JC,P = 18.9 Hz, p-Ph), 128.8 (d,
4
ArC), 132.4 (d, 2JC,P = 9.0 Hz, o-PPh), 131.4 (d, JC,P = 5.0 Hz, 3- 2JH,P = 6.6 Hz, o-Ph), 50.3 (s, NCH2), 46.6 (d, JC,P = 9.4 Hz,
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5
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ArC), 130.8 (d, JC,P = 1.9 Hz, 5-ArCH), 130.6 (d, JC,P = 5.5 Hz, CMe3), 39.3 (d, JH,P = 13.4 Hz, PCH2) 30.9 (d, JC,P = 12.8 Hz,
3-ArC), 129.4 (d, JC,P = 2.2 Hz, 6-ArC), 129.1 (d, JC,P = 3.3 Hz, CH), 29.3 (s, CMe3); 31P{1H} NMR (243 MHz, THF-d8): δ [ppm]
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5-ArC), 129.0 (d, JC,P = 2.0 Hz, 2-ArC), 128.7 (d, JC,P = 8.1 Hz, = −20.28 (s). HR-MS (FAB+): found m/z = 385.2766, calcd m/z
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m-PPh), 128.5 (s, ipso-PPh), 126.7 (d, JC,P = 2.2 Hz, 4-ArC), for C24H38N2P [MH+] = 385.2767 (Δ = −1.8 ppm).
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125.0 (s, 4-ArC), 32.3 (d, JC,P = 7.6 Hz, PCH2), 28.9 (d, JC,P
9.8 Hz, PCH2), 2.0 (s, SiMe3), 1.9 (s, SiMe3); 31P{1H} NMR 1.00 eq.) was added to a solution of [PN2]H2 (230 mg,
(243 MHz, C6D6): δ [ppm] = 8.5 (s). 600 µmol, 1.00 eq.) in toluene (4 mL) and the resulting reac-
=
[PN2]TiCl2 (6-Ti). Solid (Me2N)2TiCl2 (124 mg, 600 µmol,
bn[NPN]HfI2 (5-Hf). Following the procedure provided for tion mixture stirred for 2 h at 60 °C. The resulting dark solu-
the zirconium derivative, the title compound was prepared tion was allowed to slowly cool to room temperature. After
starting from 4-Hf (2.25 g, 3.10 mmol, 1.00 eq.) and trimethyl- approximately 2 h dark microcrystals formed and were isolated
silyl iodide (967 μl, 1.36 g, 6.8 mmol, 2.20 eq.). The product via filtration. The obtained solid was washed with pentane (2 ×
was obtained as a colourless crystalline powder (1.63 g, 1 mL) and dried in vacuum to afford the product as a red-
1.81 mmol, 59%). Elemental analysis calcd for brown crystalline powder (83 mg, 166 µmol, 27%). Elemental
C26H35HfI2N2PSi2: C 34.89, H 3.94, N 3.13, found: C 35.06, H analysis calcd for C24H35Cl2N2PTi: C 57.50, H 7.04, N 5.59,
4.10, N 3.31. 1H NMR (600 MHz, C6D6): δ [ppm] = 7.37–7.34 found: C 57.16, H 7.07, N 5.83. 1H NMR (600 MHz, CD2Cl2):
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(m, 2 H, o-PPh), 7.32 (d, JH,H = 7.9 Hz, 1 H, 6-ArH), 7.27 (dd, δ [ppm] = 7.83 (dd, JH,H = 8.3 Hz, JH,P = 7.9 Hz, 4 H, o-Ph),
3JH,H = 7.8 Hz, 4JH,H = 0.7 Hz, 1 H, 6-ArH), 7.12–7.08 (m, 1 H, 5- 7.39 (m, 4 H, m-Ph), 7.38 (m, 2 H, p-Ph), 4.25 (d, JH,H = 13.9
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ArH), 7.08–7.05 (m, 2 H, m-PPh), 7.04–7.01 (m, 1 H, p-PPh), Hz, 2 H, NCH2), 3.69 (dd, JH,H = 13.8 Hz, JH,H = 3.9 Hz, 2 H,
6.99–6.94 (m, 1 H, 5-ArH), 6.92 (d, JHH = 7.3 Hz, 1 H, 3-ArH), NCH2), 2.22 (dm, 3JH,P = 27.0 Hz, 1 H, CH), 2.72 (dd, 2JH,P = 7.3
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6.90–6.84 (m, 2 H, 4-ArH), 6.76–6.73 (m, 1 H, 3-ArH), 3.12 (dd, Hz, JH,H = 4.5 Hz, 2 H, PCH2), 1.17 (s, 18 H, CMe3); 13C{1H}
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3JH,P = 5.2 Hz, JH,H = 13.8 Hz, 1 H, PCH2), 2.87 (dd, JH,P = 4.8 NMR (151 MHz, CD2Cl2): δ [ppm] = 136.4 (d, JC,P = 14.1 Hz,
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Hz, JH,H = 12.9 Hz, 1 H, PCH2), 2.72 (t, JH,H = 13.8 Hz, 1 H, ipso-Ph), 132.4 (d, JC,P = 12.5 Hz, m-Ph), 130.3 (d, JC,P = 1.9
PCH2), 2.42 (t, 2JH,H = 12.9 Hz, 1 H, PCH2), 0.44 (s, 9 H, SiMe3), Hz, p-Ph), 129.3 (d, JC,P = 8.3 Hz, o-Ph), 64.5 (s, NCH2), 61.9
2
0.00 (s, 9 H, SiMe3); 13C{1H} NMR (151 MHz, C6D6): δ [ppm] = (d, JC,P = 4.7 Hz, CMe3), 38.7 (d, JC,P = 5.9 Hz, CH), 28.2
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146.3 (d, JC,P = 3.8 Hz, 1-ArC), 138.9 (d, JC,P = 9.6 Hz, 1-ArC), (s, CMe3), 26.0 (d, JC,P = 6.1 Hz, PCH2); 31P{1H} NMR
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135.0 (d, JC,P = 0.9 Hz, 6-ArC), 134.7 (d, JC,P = 3.2 Hz, 2-ArC), (243 MHz, CD2Cl2): δ [ppm] = −8.4 (s).
132.5 (d, JC,P = 8.5 Hz, o-PPh), 131.2 (d, JC,P = 5.2 Hz, 3-ArC),
130.8 (d, JC,P = 2.0 Hz, p-PPh), 130.6 (d, JC,P = 5.5 Hz, 3-ArC), (483 mg, 1.00 mmol, 1.00 eq.) in toluene (15 mL) was added to
130.5 (s, ipso-PPh), 129.8 (d, 4JC,P = 2.1 Hz, 6-ArC), 129.5 (d, 2JC, a stirred solution of [PN2]H2 (405 mg, 1.00 mmol, 1.00 eq.) in
P = 2.5 Hz, 2-ArC), 129.1 (d, 5JC,P = 3.3 Hz, 5-ArC), 128.9 (d, 5JC,P toluene (5 mL) over a period of 5 min. The reaction was stirred
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[PN2]ZrCl2 (6-Zr). A solution of (Me3SiCH2)2ZrCl2(OEt2)2
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= 2.1 Hz, 5-ArC), 128.6 (d, JC,P = 8.2 Hz, m-PPh), 126.2 (d, JC,P at 60 °C for 48 h then heated to 110 °C. The lightly beige sus-
= 2.2 Hz, 4-ArC), 124.8 (s, 4-ArC), 32.3 (d, JC,P = 10.3 Hz, pension was filtered hot and the resulting solution allowed to
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PCH2), 28.8 (d, JC,P = 12.3 Hz, PCH2), 2.3 (s, SiMe3), 2.0 (s, cool to room temperature resulting in the precipitation of a
SiMe3); 31P{1H} NMR (243 MHz, C6D6): δ [ppm] = 13.4 (s).
brown solid. To ensure complete precipitation of the product,
[PN2]H2. Neat diphenyl phosphine (5.0 mL, 5.40 g, the suspension was concentrated to a volume of 4 mL and the
29.0 mmol) was added to N,N′-bis-(tert-butyl)-2-(aminomethyl)- precipitate then filtered off. The obtained beige powder was
allylamine (100 mL) and the resulting mixture heated to 60 °C. washed with pentane (2 × 2 mL) and dried in vacuum to afford
Over the period of 7 d, AIBN (total amount: 250 mg, the title compound as
a pale beige powder (320 mg,
1.59 mmol, 5 mol%) was added in equal portions in intervals 0.59 mmol, 59%). In multiple attempts low carbon values
of one day. The conversion was monitored by 31P NMR were obtained upon combustional analysis (e.g. calcd for
spectroscopy and the reaction halted at conversions of approxi- C23H35Cl2N2PZr: C 52.99, H 6.48, N 5.14, found: C 51.82, H
mately 90%. The solvent was removed via distillation (130 °C, 6.42, N 5.31), possibly due to carbide formation during com-
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10−1 mbar) and reused for further preparations of the title bustion. H NMR (600 MHz, CD2Cl2): δ [ppm] = 7.87 (dd, JH,H
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compound. The residue was dissolved in pentane and filtered = 8.2 Hz, JH,P = 8.2 Hz, 4 H, o-Ph), 7.40 (m, 4 H, m-Ph), 7.38
2
through a pad of Celite. The solvent was removed in vacuum (m, 2 H, p-Ph), 3.89 (d, JH,H = 12.7 Hz, 2 H, NCH2), 3.40 (dd,
and the remaining yellow solid was washed with (Me3Si)2O 2JH,H = 12.6 Hz, JH,H = 3.1 Hz, 2 H, NCH2), 3.07 (dm, JH,P
=
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(10 mL) to remove minor amounts of Ph4P2. The remaining 31.2 Hz, 1 H, CH), 2.71 (dd, JH,P = 9.5 Hz, JH,H = 2.9 Hz, 2 H,
solid was dried in vacuum to afford the title compound as a PCH2), 1.09 (s, 18 H, CMe3); 13C{1H} NMR (151 MHz, CD2Cl2):
Dalton Trans.
This journal is © The Royal Society of Chemistry 2016