Paper
Dalton Transactions
246.1 Hz, C6F5), 133.6 (dm, JCP = 14.0 Hz, 2XCH), 124.2 (br,
(21): Yield: 470 mg (80%). Anal. Calcd for C42H3BF33P
i-C6F5), 117.2 (dd, JCP = 99.1 Hz, JCF = 13.2 Hz, Cq), 23.3 (dd, (1076.21): calcd C 42.89, H 0.26; found C 42.36, H 0.56. 1H
JCP = 5.6 Hz, JCF = 1.0 Hz, CH3), 22.6 (dd, JCF = 7.6 Hz, JCP
=
NMR (499.7 MHz, CD2Cl2, Me4Si): δ = 8.03 ppm (m, CH); 11B-
5.2 Hz, CH3), 21.7 ppm (m, CH3); 19F NMR (376.6 MHz, {1H} NMR (128.4 MHz, CD2Cl2, BF3·OEt2): δ = −16.7 ppm (s, ν1/2
1
CD2Cl2, CFCl3): δ = −115.6 (d, JPF = 940 Hz, 1F, PF), −133.1 = 26 Hz); 19F NMR (376.6 MHz, CD2Cl2, CFCl3): δ = −124.4
3
1
(m, 8F, o-C6F5), −163.8 (t, JFF = 20.3 Hz, 4F, p-C6F5), (dm, JPF = 1060 Hz, 1F, PF), −125.7 (m, 6F, o-C6F4H), −128.2
−167.6 ppm (m, 8F, m-C6F5); 31P{1H} NMR (162.0 MHz, (m, 6F, m-C6F4H), −133.3 (m, 8F, o-C6F5), −163.9 (t, JFF
=
3
CD2Cl2, H3PO4): δ = 93.0 ppm (d, 1JPF = 940 Hz). 20.3 Hz, 4F, p-C6F5), −167.8 ppm (m, 8F, m-C6F5); 31P{1H} NMR
1
(18): Yield: 431 mg (86%); Anal. Calcd for C45H21BF21P (162.0 MHz, CD2Cl2, H3PO4): δ = 70.1 ppm (dsept, JPF = 1060
(1002.41): calcd C 53.92, H 2.11; found C 54.21, H 2.21. 1H Hz, 3JPF = 8.5 Hz). 13C{1H} NMR: Could not be obtained due to
NMR (499.7 MHz, CD2Cl2, Me4Si): δ = 7.90 (m, 1H, CH), 7.68 low solubility of the compound in all common NMR solvents.
(m, 1H, CH), 7.50 (m, 1H, CH), 7.23 (m, 1H, CH), 2.47 ppm (m,
(22): This reaction was performed on a smaller scale using
3H, CH3); 11B{1H} NMR (128.4 MHz, CD2Cl2, BF3·OEt2): δ = 32 mg (820 μmol) of (C6F5)Ph2PF2 and using 100 mg of 8
−16.7 ppm (s, ν1/2 = 26 Hz); 13C{1H} NMR (125.7 MHz, CD2Cl2, (813 μmol) as opposed to [Et3Si][B(C6F5)4] to abstract a fluoride
1
Me4Si): δ = 148.5 (d, JCF = 240.5 Hz, C6F5), 145.4 (dd, JCP = 8.5 ion. Yield: 71 mg (83%). Anal. Calcd for C42H10BF26P
1
Hz, JCF = 1.5 Hz, CH), 138.6 (d, JCF = 244.0 Hz, C6F5), 137.7 (1050.28): calcd C 48.03, H 0.96; found C 47.45, H 1.17. 1H
1
(dd, JCP = 2.7 Hz, JCF = 1.3 Hz, CH), 136.7 (d, JCF = 242.0 Hz, NMR (CD2Cl2, 400 MHz, Me4Si): δ 8.15 (m, 2H, p-C6H5), 7.89
C6F5), 135.6 (dd, JCP = 18.4 Hz, JCF = 2.2 Hz, CH), 134.5 (d, JCP
=
(m, 8H, o, m-C6H5). 11B NMR (CD2Cl2, 128 MHz, BF3·OEt2):
12.0 Hz, CH), 128.3 (d, JCP = 15.7 Hz, CH), 124.1 (br, i-C6F5), δ −16.7 (s, B(C6F5)4) 19F NMR (CD2Cl2, 377 MHz, CFCl3):
1
2
115.7 (dd, JCP = 105.2 Hz, JCF = 12.8 Hz, Cq), 22.0 (dd, JCP
=
δ −123.54 (dt, 1JPF = 1023 Hz, 4JFF = 19 Hz, 1F, PF), −123.83 (m,
5.0 Hz, JCF = 2.8 Hz, CH3); 19F NMR (376.6 MHz, CD2Cl2, 2F, P(o-C6F5)), −130.13 (m, 1F, P(p-C6F5)), −133.18 (m, 8F, B(o-
1
3
CFCl3): δ = −125.5 (d, JPF = 993 Hz, 1F, PF) −133.0 (m, 8F, C6F5)), −152.80 (m, 2F, P(m-C6F5)), −163.75 (t, JFF = 20 Hz, 4F,
o-C6F5), −163.6 (t, JFF = 20.2 Hz, 4F, p-C6F5), −167.5 ppm (m, B(p-C6F5)), −167.65 (t/br, JFF = 19 Hz, 8F, B(m-C6F5)). 31P{1H}
3
3
8F, m-C6F5); 31P{1H} NMR (162.0 MHz, CD2Cl2, 25 °C): δ = NMR (CD2Cl2, 162 MHz, H3PO4): δ 87.6 (dt, 1JPF = 1023 Hz, 3JPF
103.2 ppm (d, 1JPF = 993 Hz).
= 7 Hz PF). 13C{1H} NMR: (CD2Cl2, 100 MHz, Me4Si): δ 148.5
1
1
(19): Yield: 384 mg (80%); Anal. Calcd for C22H15BF21P (d, JCF = 240 Hz, C6F5), 140.59 (CH aromatic), 138.6 (d, JCF
=
=
(960.33): calcd C 52.53, H 1.57; found C 52.53, H 1.52. 1H NMR 246 Hz, C6F5), 136.7 (d, JCF = 245 Hz, C6F5), 134.0 (d, JPC
(499.7 MHz, CD2Cl2, Me4Si): δ = 8.06 (m, 1H, CH), 7.08 ppm 14 Hz), 131.8 (d, 3JPC = 15 Hz, CH aromatic).
(m, 4H, CH); 11B{1H} NMR (128.4 MHz, CD2Cl2, BF3·OEt2): δ =
1
2
−16.7 ppm (s, ν1/2 = 26 Hz); 13C{1H} NMR (125.7 MHz, CD2Cl2,
X-ray data collection, reduction, solution and refinement
1
1
Me4Si): δ = 148.5 (d, JCF = 240.5 Hz, C6F5), 138.6 (d, JCF
=
Single crystals were coated in Paratone-N oil in the glove-box,
mounted on a MiTegen Micromount and placed under an N2
stream. The data were collected on a Bruker Apex II diffracto-
meter. The data were collected at 150( 2) K for all crystals.
Data reduction was performed using the SAINT software
package, and an absorption correction was applied using
SADABS. The structures were solved by direct methods using
XS and refined by full-matrix least squares on F2 using XL as
implemented in the SHELXTL suite of programs. All non-
hydrogen atoms were refined anisotropically. Carbon-bound
hydrogen atoms were placed in calculated positions using an
appropriate riding model and coupled isotropic temperature
factors.
244.0 Hz, C6F5), 139.0 (dd, JCP = 2.8 Hz, JCF = 1.7 Hz, CH),
1
136.7 (d, JCF = 242.0 Hz, C6F5), 134.3 (d, JCP = 14.5 Hz, CH),
131.3 (d, JCP = 14.5 Hz, CH), 124.3 (br, i-C6F5), 116.5 ppm
(dd, JCP = 108.9 Hz, JCF = 14.5 Hz, i-C6H5); 19F NMR
1
(376.6 MHz, CD2Cl2, CFCl3):
δ
=
−128.2 (d, JPF
=
=
3
997.8 Hz, 1F, PF), −133.0 (m, 8F, o-C6F5), −163.6 (t, JFF
20.3 Hz, 4F, p-C6F5), −167.5 ppm (m, 8F, m-C6F5); 31P{1H}
1
NMR (162.0 MHz, CD2Cl2, H3PO4): δ = 94.8 ppm (d, JPF
=
997.8 Hz).
(20): Yield: 451 mg (89%); Anal. Calcd for C42H12BF24P
(1014.04): calcd C 49.73, H 1.19; found C 49.69, H 0.87. 1H
NMR (499.7 MHz, CD2Cl2, Me4Si): δ = 7.80 (m, 2H, CH),
7.54 ppm (m, 2H, CH); 11B{1H} NMR (128.4 MHz, CD2Cl2,
BF3·OEt2): δ = −16.7 ppm (s, ν1/2 = 26 Hz); 13C{1H} NMR
1
(125.7 MHz, CD2Cl2, Me4Si): δ = 169.6 (ddd, JCF = 242.0 Hz,
Results and discussion
Synthesis
1
JCP = 3.27 Hz, JCF = 1.60 Hz, CF), 148.5 (d, JCF = 240.5 Hz,
1
C6F5), 138.6 (d, JCF = 244.0 Hz, C6F5), 137.7 (ddd, JCP = 15.2
1
Hz, JCF = 10.8 Hz, JCF = 1.0 Hz, CH), 136.7 (d, JCF = 242.0 Hz, The careful addition of a CD2Cl2 solution containing 1 : 1
C6F5), 124.1 (br, i-C6F5), 119.7 (dd, JCP = 22.8 Hz, JCF = 16.1 Hz, tBu3P/B(C6F5)3 to XeF2 at ambient temperature immediately
1
2
4
CH), 112.0 ppm (ddd, JCP = 116.1 Hz, JCF = 15.7 Hz, JCF
=
resulted in vigorous effervescence to produce the fluorophos-
3.4 Hz, Cq); 19F NMR (376.6 MHz, CD2Cl2, CFCl3): δ = −92.3 phonium fluoroborate salt, [tBu3PF][FB(C6F5)3] (1; Scheme 1),
(m, 3F, CF), −122.9 (d, 1JPF = 1000 Hz, 1F, PF) −133.1 (m, 8F, o- which could be isolated in quantitative yield as a colourless,
C6F5), −163.6 (t, 3JFF = 20.2 Hz, 4F, p-C6F5), −167.5 ppm (m, 8F, analytically pure solid. 31P{1H} NMR spectroscopy of the result-
m-C6F5); 31P{1H} NMR (162.0 MHz, CD2Cl2, H3PO4): δ = ing mixture shows a doublet signal at δ 148.5 ppm (1JPF = 1019
94.8 ppm (dd, 1JPF = 1000 Hz, 5JPF = 1.8 Hz).
Hz), while the 19F NMR spectrum shows the corresponding
Dalton Trans.
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