Synthesis and ReactiWity of Fluoro Complexes
C and H analyses of different samples were in agreement with the
amount of water determined by integration of the 1H NMR spectra.
Anal. Calcd for [RhF(COD)(PCy3)]‚0.4H2O, C26H45.8FO0.4PRh: C,
60.32; H, 8.92. Found: C, 60.61; H, 9.30.
2630, 1842 (both s) (FHF). Anal. Calcd for C26H28F2PRh: C, 60.95;
H, 5.51. Found: C, 60.91; H, 5.81.
[Rh(FHF)(COD)(PiPr3)] (12). A solution of complex 5 (180
mg, 0.46 mmol) in THF (10 mL) was treated with NEt3‚3HF (26
µL, 0.16 mmol) at room temperature. The mixture was stirred for
50 min, and the volatiles were removed in vacuo. The residue was
extracted with Et2O (15 mL), the extract was filtered, and the solvent
was evaporated to dryness in vacuo. The residue was washed with
n-pentane (3 × 2 mL) at 0 °C and dried in vacuo to give 12 as a
yellow solid. Yield: 174 mg, 92%. Mp 87-92 °C. 1H NMR (200.1
MHz, CD2Cl2, 21 °C): δ 11.7 (v br s, 1 H, FHF), 5.02 (m, 2 H,
CH, COD), 3.42 (m, 2 H, CH, COD), 2.47-2.24 (m, 4 H, CH2),
NMR Data of 7. 19F NMR (282.2 MHz, C6D6): δ -280.2 (ddt,
2
2
1JRhF ) 56.7 Hz, JPFtrans ) 176.9 Hz, JPFcis ) 28.8 Hz). 31P{1H}
NMR (121.4 MHz, C6D6): δ 44.9 (ddt, P trans to F, 1JRhP ) 179.7
2
1
Hz, JPP ) 41.6 Hz), 24.8 (ddd, P trans to P, JRhP ) 141.4 Hz).
NMR Data of 9. 19F NMR (188.3 MHz, C6D6): δ -277.0 (ddt,
2
2
1JRhF ) 74.6 Hz, JPFtrans ) 174.4 Hz, JPFcis ) 29.8 Hz). 31P{1H}
1
NMR (81.0 MHz, C6D6): δ 56.8 (ddt, P trans to F, JRhP ) 173.1
2
1
Hz, JPP ) 39.5 Hz), 32.1 (ddd, P cis to P, JRhP ) 153.4).
[RhF(NBD)(PiPr3)] (10). A suspension of [Rh(µ-OMe)(NBD)]2
(194 mg, 0.43 mmol) in THF (12 mL) was treated with NEt3‚3HF
(47 µL, 0.29 mmol) at room temperature. The yellow solution was
stirred for 1 h and 40 min, and then PiPr3 (164 µL, 0.86 mmol)
was added. The mixture was stirred for 30 min, and the volatiles
were removed in vacuo. The residue was stirred with Et2O (3 mL)
to give a yellow solid, which was washed with Et2O (2 × 3 mL)
and dried in vacuo, giving spectroscopically pure 10. Yield: 210
2.13-1.79 (m, 7 H, P-CH and CH2), 1.29 (dd, 18 H, Me, 3JPH
)
13.4 Hz, 3JHH ) 7.2 Hz); (-80 °C): δ 12.5 (br dd, 1 H, FHF, 1JFH
) 366.2 and 32.0 Hz). 13C{1H} NMR (50.3 MHz, C6D6, 24 °C):
1
2
δ 104.3 (dd, CH, COD, JRhC and JPC ) 10.9 and 3.5 Hz), 62.9
1
2
(dd, CH, COD, JRhC and JPC ) 15.3 and 1.6 Hz), 33.6 (d, CH2,
2JRhC ) 2.6 Hz), 27.7 (d, CH2, 2JRhC ) 1.6 Hz), 22.6 (d, P-C, 1JPC
) 17.1 Hz), 19.7 (s, Me). 19F NMR (188.3 MHz, CD2Cl2, 21 °C):
δ -180.7 (br s, Rh-FHF), -259.6 (br s, Rh-FHF); (-80 °C): δ
-176.3 (dd, Rh-FHF, 1JFH ) 363.8 Hz, 2JFF ) 133.9 Hz), -256.7
(m, Rh-FHF). 31P{1H} NMR (81 MHz, CD2Cl2, 21 °C): δ 39.1
(d, JRhP ) 147.7 Hz); (-80 °C): δ 38.3 (dd, JRhP ) 146.6 Hz,
2JPF ) 12.7 Hz). IR (Nujol, cm-1): 2580, 1866 (both s) (FHF).
Anal. Calcd for C17H34F2PRh: C, 49.76; H, 8.53. Found: C, 49.59;
H, 8.74.
1
mg, 65%. Dec pt 122-124 °C. H NMR (200.1 MHz, C6D6): δ
5.19 (m, 2 H, CHdCH), 3.45 (m, 2 H, aliphatic CH, NBD), 3.05
(m, 2 H, CHdCH), 1.77 (m, 3 H, P-CH), 1.14 (dd, 18 H, Me,
3JPH ) 13.4 Hz, 3JHH ) 7.0 Hz), the signals of the CH2 protons are
overlapped with the Me signal. 13C{1H} NMR (50.3 MHz, C6D6):
δ 84.2 (dd, CHdCH, JRhC and JPC ) 10.6 and 5.8 Hz), 62.8 (dd,
CH2, NBD, JRhC and JPC ) 5.1 and 1.5 Hz), 51.1 (dd, aliphatic
CH, NBD, JRhC and JPC ) 2.6 and 1.5 Hz), 42.8 (d, CHdCH, 1JRhC
) 12.1 Hz), 23.0 (dd, C-P, 1JPC ) 17.9 Hz, 2JRhC ) 1.1 Hz), 19.8
1
1
[Rh(FHF)(COD)(PCy3)] (13). A solution of complex 6 (147
mg, 0.29 mmol) in THF (7 mL) was treated with NEt3‚3HF (16
µL, 0.098 mmol) at room temperature. The mixture was stirred for
1 h, and then the volatiles were removed in vacuo at 40 °C for 2
h. The residue was extracted with Et2O (15 mL). The extract was
filtered, concentrated up to ca. 3 mL in vacuo, and stored at -20
°C for 24 h. A yellow solid crystallized, which was washed with
cold (-20 °C) Et2O (2 × 2 mL) and dried in vacuo. Yield: 120
mg, 78%. Dec pt 102-105 °C. 1H NMR (200.1 MHz, CD2Cl2, 24
°C): δ ca. 12 (very broad s, FHF), 4.99 (m, 2 H, CH, COD), 3.31
(m, 2 H, CH, COD), 2.37, 1.93-1.61, 1.26-1.15 (all m, 41 H,
2
(d, Me, JPC ) 1.1 Hz). 19F NMR (188.3 MHz, C6D6, 22 °C): δ
-230.2 (br s); (D8-toluene, -80 °C): δ -224.7 (br d, 1JRhF ) 69.7
1
Hz). 31P{1H} NMR (81.0 MHz, C6D6, 22 °C): δ 42.4 (d, JRhP
)
1
177.0 Hz); (D8-toluene, -80 °C): δ 42.2 (dd, JRhP ) 177.8 Hz,
2JPF ) 9.4 Hz). Anal. Calcd for C16H29FPRh: C, 51.34; H, 7.81.
Found: C, 50.79; H, 7.54. Combustion analysis were performed
on a spectroscopically pure, crystalline (recrystallized from CH2-
Cl2/Et2O/n-hexane) sample. In our opinion, the difference in %C
(0.55; 1% relative error) is due to a combustion problem and not
to the impurity of the sample.
1
COD CH2 and Cy). H NMR (200.1 MHz, CD2Cl2, -80 °C): δ
12.50 (br dd, 1JFH ) 364.2 and 32.0 Hz, FHF). 13C{1H} NMR (50.3
1
2
MHz, C6D6): δ 104.0 (dd, COD CH, JRhC and JPC ) 7.4 and
[Rh(FHF)(COD)(PPh3)] (11). A solution of complex 3 (177
mg, 0.36 mmol) in THF (12 mL) was treated with NEt3‚3HF (25
µL, 0,15 mmol) at room temperature. The mixture was stirred for
1 h, and the volatiles were removed in vacuo for 2 h. The yellow
residue was dissolved in THF (3 mL) in a Schlenk tube, and a
layer of n-hexane (13 mL) was added slowly to minimize the mixing
with the THF solution. The tube was not moved until the diffusion
of both solvents was complete. Yellow crystals grew that were
washed with n-pentane (3 × 3 mL) and dried in vacuo. Yield: 123
1
2
10.7 Hz), 63.1 (dd, COD CH, JRhC and JPC ) 1.5 and 15.3 Hz),
2
1
33.7 (d, COD CH2, JRhC ) 2.4 Hz), 32.6 (d, C-P, JPC ) 17.3
Hz), 30.5 (s, Cy), 28.0, 27.8, 26.8 (all s, COD CH2 and Cy). 19F
NMR (188.3 MHz, CD2Cl2, 24 °C): δ -180.5 (br s, Rh-FHF),
-261.2 (br s, Rh-FHF); (-80 °C): δ -176.2 (dd, 1JFH ) 359.7,
2JFF ) 137.5 Hz, Rh-FHF), -258.3 (m, Rh-FHF). 31P{1H} NMR
1
(81.0 MHz, CD2Cl2, 24 °C): δ 28.0 (d, JRhP ) 146.7 Hz); (-80
1
2
°C): δ 27.7 (dd, JRhP ) 145.3 Hz, JPF ) 12.9 Hz). IR (Nujol,
cm-1): 2634 and 1842 (FHF). Anal. Calcd for C26H46F2PRh: C,
58.86; H, 8.74. Found: C, 58.13; H, 9.00. Small amounts of NEt3‚
3HF that could not be completely removed in vacuo are likely
responsible for the difference in the C percentage.
1
mg, 67%. Dec pt 138-141 °C. H NMR (200.1 MHz, C6D6, 24
°C): δ 11.7 (very br s, 1 H, FHF), 7.84-7.74 (m, 6 H, Ph), 7.02
(m, 9 H, Ph), 5.76 (m, 2 H, CH, COD), 2.83 (m, 2 H, CH, COD),
2.20 (m, 4 H, CH2), 1.59-1.39 (m, 4 H, CH2); (CD2Cl2, -80 °C):
δ 12.24 (dd, 1 H, FHF, 1JFH ) 375.3 and 41.0 Hz). 13C{1H} NMR
(50.3 MHz, C6D6, 24 °C): δ 134.7 (d, Ph, JPC ) 11.8 Hz), 131.4
Single-Crystal X-ray Structure Determinations of Complexes
3 and 11. The crystals were mounted in inert oil on a glass fiber
and transferred to the diffractometer (Siemens P4 with LT2 low-
temperature attachment) as summarized in Table 1. The structures
were solved by the heavy-atom method and were refined aniso-
tropically on F2 (program SHELX-93, G. M. Sheldrick, University
of Go¨ttingen). For complex 3, unit cell parameters were determined
from a least-squares fit of 88 accurately centered reflections (10.82
< 2θ < 2 5.00). Maximum ∆/σ ) -0.003, maximum ∆F ) 0.372
e Å-3. Hydrogen atoms were included using a riding method. For
complex 11, unit cell parameters were determined from a least-
1
(d, C-P, JPC ) 39.0 Hz), 130.8 (d, Ph, JPC ) 2.2 Hz), 128.7 (d,
1
2
Ph, JPC ) 10.0 Hz), 106.6 (dd, CH, COD, JRhC and JRhP ) 9.6
and 7.5 Hz), 65.6 (d, CH, COD, 1JRhC ) 15.0 Hz), 33.4, 28.2 (both
s, CH2). 19F NMR (188.3 MHz, C6D6, 77 °C): δ -225 (br s); (CD2-
Cl2, 25 °C): δ -190 (very br s, Rh-FHF), -260 (very br s, Rh-
FHF); (CD2Cl2, -80 °C): δ -177.3 (dd, Rh-FHF, 1JFH ) 372.8
Hz, 1JFF ) 124.3 Hz), -258.3 (m, Rh-FHF). 31P{1H} NMR (81.0
MHz, CD2Cl2, 25 °C): δ 26.1 (d, 1JRhP ) 154.9 Hz); (-80 °C): δ
1
2
27.0 (dd, JRhP ) 154.1 Hz, JPF ) 17.2 Hz). IR (Nujol, cm-1):
Inorganic Chemistry, Vol. 43, No. 18, 2004 5673