Dalton Transactions
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(δ-CH2). 31P{1H} NMR (243 MHz, 299 K, benzene-d6): δ31P: NMR (151 MHz, 299 K, benzene-d6): δ13C: 146.5 (d, JPC
=
=
+
−87.6 (ν1/2 ≈ 1 Hz).
15.5 Hz, o-mes), 142.9 (d, 4JPC = 3.2 Hz, p-mes), 142.4 (d, 4JPC
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3.0 Hz, vCH), 142.0 (d, JPC = 6.2 Hz, o′-mes), 132.4 (d, JPC
Preparation of compound 12a
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3JPC = 26.0 Hz, C3), 132.1 (d, JPC = 13.0 Hz, m-mes), 131.3 (d,
Compound 9a (90 mg, 0.32 mmol, 1 eq.) and HB(C6F5)2 3JPC = 10.3 Hz, m′-mes), 127.7 (d, JPC
+
3JPC = 14.9 Hz, C4),
2
3
1
(110 mg, 0.32 mmol, 1 eq.) were suspended in pentane (5 mL) 119.3 (d, JPC = 4.7 Hz, Cv), 117.2 (d, JPC = 84.8 Hz, i-mes),
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at rt and stirred overnight. Then the insolubles were filtered 113.4 (d, JPC = 25.7 Hz, Cu), 92.4 (br m, C2), 76.8 (d, JPC
=
=
1
3
off at rt and washed with pentane (1 mL) three times. The 159.4 Hz, PCu), 48.7 (d, JPC = 61.4 Hz, C5), 30.7 (d, JPC
combined organic phases (brown solution) were cooled to 7.2 Hz, C9)t, 27.5 (m, C6)t, 27.5 (m, β-CH2)t, 26.6 (C8)t, 26.2 (d,
−95 °C and the resulting precipitate was allowed to sediment 3JPC = 13.9 Hz, C7)t, 26.0 (γ′-CH2)t, 25.3 (d, 3JPC = 5.8 Hz, o′-CH3mes),
for 1 h at −95 °C. Subsequently the supernatant solution was 23.2 (br, o-CH3mes), 21.8 (γ-CH2)t, 21.0 (δ-CH2)t, 20.7 (d, JPC
=
5
removed by cannula filtration. Drying of the residue in vacuo 1.5 Hz, p-CH3mes), [C6F5 not listed; t tentatively assigned]. 11B{1H}
yielded compound 12a as a yellow-brown powder (140 mg, NMR (192 MHz, 299 K, benzene-d6): δ11B: 34.0 (ν1/2 ≈ 850 Hz).
70%). Anal. calc. for C31H22BF10P: C, 59.45; H, 3.45. Found C, 19F NMR (564 MHz, 299 K, benzene-d6): δ19F: −128.6 (m, 2F,
58.77; H, 3.48. IR (KBr) ˜ν [cm−1] = 2168 (νCuC). M.p. 50 °C. o-C6F5A), −131.8 (m, 2F, o-C6F5B), −157.3 (t, JFF = 20.6 Hz, 1F,
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Decomp. >80 °C. H NMR (600 MHz, 299 K, benzene-d6): δ1H: p-C6F5B), −158.6 (t, JFF = 20.5 Hz, 1F, p-C6F5A), −163.6 (m, 2F,
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3
4
3
6.50 (dm, JPH = 4.6 Hz, 2H, m-mes), 6.36 (dm, JPH
+
4JPH
=
m-C6F5B), −164.5 (m, 2F, m-C6F5A), [Δδ19Fmp = 5.9 HzA,
44.3 Hz, 1H, H3), 5.34 (sext, JHH ≈ JHH ≈ JPH = 1.1 Hz, 1H, 6.3 HzB]. 31P NMR (243 MHz, 299 K, benzene-d6): δ31P: 15.4
4
2
5
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vCH2Z), 4.99 (m, 1H, vCH2E), 2.59 (dm, JPH = 9.4 Hz, 2H, (ca. 94%, d, JPH
H5), 2.36 (s, 6H, o-CH3mes), 1.94 (s, 3H, p-CH3mes), 1.62 (m, 3H, ν1/2 ≈ 65 Hz).
4-CH3), 1.56 (tm, 4JHH ≈ 4JHH = 1.2 Hz, 3H, CH3). 13C{1H} NMR
+
4JPH = 41.4 Hz), 18.0 (impurity, ca. 6%,
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Preparation of compound 14b
(151 MHz, 299 K, benzene-d6): δ13C: 143.8 (d, JPC = 11.4 Hz,
o-mes), 143.5 (d, JPC = 3.2 Hz, p-mes), 135.9 (d, JPC + JPC
4
2
3
=
Compound 10b (115 mg, 0.25 mmol, 1 eq.) and HB(C6F5)2
24.6 Hz, C3), 131.7 (d, JPC = 12.0 Hz, m-mes), 127.8 (vCH2)a, (87 mg, 0.25 mmol, 1 eq.) were suspended in pentane (3 mL)
125.0 (d, 3JPC = 4.4 Hz, Cv), 118.5 (d, 2JPC + 3JPC = 13.5 Hz, C4), at rt and then stirred overnight. Subsequently the reaction
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116.8 (d, JPC = 92.8 Hz, i-mes), 113.3 (d, JPC = 24.7 Hz, Cu), mixture was cooled to −35 °C for precipitation. The green
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1
94.7 (br, C2), 79.3 (d, JPC = 147.2 Hz, PCu), 40.6 (d, JPC
=
supernatant solution was removed by decantation and the
64.6 Hz, C5), 22.6 (d, JPC = 4.6 Hz, o-CH3mes), 21.1 (CH3), 20.6 residue was washed with pentane (1 mL) at −35 °C twice.
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(d, JPC = 1.6 Hz, p-CH3mes), 18.2 (d, JPC
+
4JPC = 11.2 Hz, Drying of the residue in vacuo yielded compound 14b as a
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4-CH3), [not listed C6F5; afrom ghsqc]. 11B{1H} NMR (192 MHz, yellow-green solid. Concentration of the filtrate and a second
299 K, benzene-d6): δ11B: 33.5 (ν1/2 ≈ 600 Hz). 19F NMR crystallization at −35 °C yields another 20 mg of compound
(564 MHz, 299 K, benzene-d6): δ19F: −129.0 (m, 2F, o-C6F5A), 14b (overall: 140 mg, 70%). Anal. calc. for C43H42BF10P: C,
−131.9 (m, 2F, o-C6F5B), −156.9 (t, JFF = 20.6 Hz, 1F, p-C6F5B), 65.33; H, 5.35. Found C, 65.16; H, 5.35. IR (KBr) ˜ν [cm−1] =
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−158.7 (t, JFF = 20.3 Hz, 1F, p-C6F5A), −163.7 (m, 2F, m-C6F5B), 2163 (νCuC). M.p. 160 °C. H NMR (600 MHz, 299 K, benzene-
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−164.5 (m, 2F, m-C6F5A), [Δδ19Fmp = 5.8 HzA, 6.8 HzB]. d6): δ1H: 7.24 (dd, JPH = 4.7 Hz, JHH = 1.8 Hz, 1H, m-tipp),
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4
3
4
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31P NMR (243 MHz, 299 K, benzene-d6): δ31P: 11.4 (dm, JPH
+
7.07 (dd, JPH = 3.9 Hz, JHH = 1.8 Hz, 1H, m′-tipp), 6.45 (dm,
3JPH + 4JPH = 40.7 Hz, 1H, H3), 6.21 (m, 1H, vCH), 3.88 (m, 1H,
o-CHtipp), 3.77 (m, 1H, o′-CHtipp), 3.35 (m, 1H, H5), 2.71 (sept,
3JHH = 6.9 Hz, 1H, p-CHtipp), 2.43/1.92 (each m, each 1H,
4JPH = 44.3 Hz).
Preparation of compound 14a
HB(C6F5)2 (95 mg, 0.28 mmol, 1 eq.) was added to a solution 9-CH2)t, 1.98/1.88 (each m, each 1H, β-CH2)t, 1.74 (m, 2H,
of compound 9b (105 mg, 0.28 mmol, 1 eq.) in pentane (3 mL) γ′-CH2)t, 1.65 (d, JHH = 6.4 Hz, 3H, o-CH3tipp), 1.63/1.22 (each
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at rt and the reaction mixture was stirred overnight. Then the m, each 1H, 6-CH2)t, 1.50/0.99 (each m, each 1H, 8-CH2)t, 1.46/
insolubles were removed by filtration and were washed with 1.00 (each m, each 1H, 7-CH2)t, 1.30 (m, 2H, γ-CH2)t, 1.23 (d,
pentane (1 mL) twice at rt. The filtrates were combined and all 3JHH = 6.4 Hz, 3H, o′-CH3tipp), 1.21 (m, 2H, δ-CH2)t, 1.20/1.19
volatiles were removed in vacuo to give compound 14a as a (each d, each 3JHH = 6.9 Hz, each 3H, p-CH3tipp), 1.09 (d, 3JHH
=
green solid (140 mg, 70%). Anal. calc. for C37H30BF10P: C, 6.7 Hz, 3H, o-CH3′tipp), 1.01 (d, JHH = 6.7 Hz, 3H, o′-CH3′tipp),
62.91; H, 4.28. Found C, 62.38; H, 4.26. IR (KBr) ˜ν [cm−1] = [ttentatively assigned]. 13C{1H} NMR (151 MHz, 299 K,
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2162 (νCuC). Decomp. >80 °C. 1H NMR (600 MHz, 299 K, benzene-d6): δ13C: 158.1 (d, JPC = 16.4 Hz, o-tipp), 154.3 (d,
2
benzene-d6): δ1H: 6.70 (m, 1H, m-mes), 6.52 (m, 1H, m′-mes), 4JPC = 3.1 Hz, p-tipp), 154.0 (d, JPC = 6.9 Hz, o′-tipp), 142.6 (d,
2
6.35 (dm, JPH + JPH = 41.4 Hz, 1H, H3), 6.22 (m, 1H, vCH), 4JPC = 3.1 Hz, vCH), 133.4 (d, JPC + JPC = 25.5 Hz, C3), 125.7
3
4
2
3
3.14 (m, 1H, H5), 2.84 (s, 3H, o-CH3mes), 2.39/1.88 (each m, (d, JPC + JPC = 14.9 Hz, C4), 124.7 (d, JPC = 13.0 Hz, m-tipp),
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3
3
each 1H, 9-CH2)t, 2.38 (s, 3H, o′-CH3mes), 2.00/1.94 (each m, 123.4 (d, JPC = 10.2 Hz, m′-tipp), 119.1 (d, JPC = 4.6 Hz, Cv),
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3
each 1H, β-CH2)t, 1.94 (s, 3H, p-CH3mes), 1.72 (m, 2H, γ′-CH2)t, 117.2 (d, JPC = 84.4 Hz, i-tipp), 111.6 (d, JPC = 25.3 Hz, Cu),
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1.48/0.96 (each m, each 1H, 8-CH2)t, 1.36/0.95 (each m, each 95.2 (br dm, J ≈ 64 Hz, C2), 77.3 (d, JPC = 160.9 Hz, PCu),
1
1
3
1H, 7-CH2)t, 1.35/0.95 (each m, each 1H, 6-CH2)t, 1.29 (m, 2H, 48.6 (d, JPC = 60.3 Hz, C5), 34.5 (p-CHtipp), 33.0 (d, JPC
=
γ-CH2)t, 1.20 (m, 2H, δ-CH2)t, [ttentatively assigned]. 13C{1H} 6.3 Hz, o′-CHtipp), 31.3 (d, JPC = 6.0 Hz, o-CHtipp), 30.5
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This journal is © The Royal Society of Chemistry 2014
Dalton Trans., 2014, 43, 632–638 | 637