10.1002/ejic.201901057
European Journal of Inorganic Chemistry
3
Analytical data for 4a. Yellow solid. 1H NMR (399.95 MHz, DMSO-d6): δ
= 1.22 (d of vt, J1 ≈ J2 ≈ 7.3 Hz, 12 H, CHMe2), 1.35 (d of vt, J1 ≈ J2 ≈ 7.5
Fur), 7.30 (br s, 8 H, NH2 of guanidinium), 7.85 (t, JHH = 5.3 Hz, 2 H,
CH2NH), 8.07 (s, 4 H, Fur) ppm. 13C{1H} NMR (100.58 MHz, DMSO-d6):
δ = 69.59 (s, CH of fc), 70.27 (vt, J′ = 30 Hz, Cipso–P of fc), 70.45 (s, CH
3
Hz, 12 H, CHMe2), 2.74 (m, 4 H, CHMe2), 4.14 (d, JHH = 5.2 Hz, 4 H,
CH2NH), 4.35 (vt, J′ = 1.8 Hz, 4 H, fc), 4.37 (vt, J′ = 1.8 Hz, 4 H, fc), 4.56
(vt, J′ = 1.8 Hz, 4 H, fc), 4.67 (vt, J′ = 1.7 Hz, 4 H, fc), 7.32 (br s, 8 H, NH2
of guanidinium), 7.88 (s, 2 H, CH2NH) ppm. 13C{1H} NMR (100.58 MHz,
DMSO-d6): δ = 18.65 (s, CHMe), 20.02 (s, CHMe), 25.47 (vt, J′ = 13 Hz,
CHMe), 39.87 (s, CH2NH), 69.30 (s, CH of fc), 70.70 (s, CH of fc), 71.30
(vt, J′ = 3 Hz, s, CH of fc), 73.73 (vt, J′ = 5 Hz, s, CH of fc), 74.64 (vt, J′ =
19 Hz, s, Cipso–P of fc), 84.44 (s, Cipso–CH2 of fc), 156.67 (s, Cipso of
guanidinium), 188.37 (dt, 1JRhC = 74 Hz, 2JPC = 16 Hz, C≡O) ppm. 31P{1H}
NMR (161.90 MHz, DMSO-d6): δ = 38.2 (d, 1JRhP = 122 Hz, P(iPr)2) ppm.
FTIR (Nujol): νmax 3319 m, 3245 m, 3134 s, 1947 s, 1935 sh, 1707 w,
1663 s, 1653 s, 1341 w, 1305 w, 1252 w, 1226 w, 1195 w, 1161 m, 1092
w, 1041 sh, 1030 m, 928 w, 885 w, 834 m, 820 w, 665 m, 629 m, 616 w,
603 w, 580 m, 545 w, 535 w, 485 m cm–1. MS (ESI+): m/z 293 ([M –
3Cl]3+), 439 ([M – 2Cl – HCl]2+), 877 ([M – Cl – 2HCl]+), 913 ([M – Cl –
HCl]+). Anal. Calcd. for C37H58Cl3Fe2N6OP2Rh·½Me2CO·½H2O (1023.9):
C 45.17, H 6.10, N 8.21%. Found C 44.93, H 5.77, N 8.00%.
of fc), 72.61 (s, CH of fc), 74.58 (vt, J′ = 6 Hz, CH of fc), 85.14 (s, Cipso
–
CH2 of fc), 111.04 (s, CH of Fur), 122.10 (vt, J′ = 16 Hz, CH of Fur),
146.61 (vt, J′ = 36 Hz, Cipso of Fur), 148.37 (s, CH of Fur), 156.64 (s, Cipso
1
of guanidinium), 184.92 (d, JRhC ≈ 62 Hz, C≡O) ppm. The signal due to
the methylene spacer is probably obscured by the solvent resonance.
31P{1H} NMR (161.90 MHz, DMSO-d6): δ = –10.9 (d, JRhP = 132 Hz,
1
PFur2) ppm. FTIR (Nujol): νmax 3110 s, 1982 s, 1663 s, 1647 s, 1550 w,
1366 m, 1341 w, 1308 w, 1236 w, 1213 w, 1196 w, 1168 m, 1121 m,
1062 w, 1028 w, 1009 s, 907 w, 883 w, 833 w, 750 m, 650 w, 621 w, 593
w, 573 m, 534 m, 489 s, 475 sh cm–1. MS (ESI+): m/z 422
([Fur2PfcCH2NHC(NH2)2]+), 438 ([Fur2POfcCH2NHC(NH2)2]+), 487 ([M –
2Cl – HCl]2+), 505 ([M – 2Cl]2+), 973 ([M – Cl – 2HCl]+). Anal. Calcd. for
C41H42Cl3Fe2N6O5P2Rh·½Me2CO·½H2O (1119.8): C 45.59, H 4.14, N
7.51%. Found C 45.51, H 4.21, N 7.00%.
Pd-catalysed cross-coupling of acyl chlorides with boronic acids. In
a typical reaction, a dry Schlenk flask was charged successively with the
respective aroyl chloride (1.25 mmol), boronic acid (1.0 mmol), sodium
carbonate (1.0 mmol) and ligand (1.1 µmol). An argon atmosphere was
established, and the flask was stoppered with a septum. Deuterated
benzene (1.8 mL), deaerated water (2.0 mL) and, finally, a 5 mM solution
of palladium(II) acetate in deuterated benzene (0.2 mL, 1.0 µmol) were
introduced. The resulting mixture was vigorously stirred at 50°C for 60
minutes. After cooling to room temperature, the mixture was diluted with
water (5 mL) to dissolve the crystallizing ionic components and
(trifluoromethyl)benzene (146.1 mg, 1.0 mmol) was added as an internal
standard. Conversions were determined by integration of 19F NMR
spectra recorded in filtered benzene phase (PTFE syringe filter, 0.45 µm
pore size). Characterisation data of the coupling products are given in
Supporting Information.
Analytical data for 4b. Yellow solid. 1H NMR (399.95 MHz, DMSO-d6): δ
= 1.06-1.34 (m, 12 H, Cy), 1.40-1.55 (m, 8 H, Cy), 1.60-1.69 (m, 4 H, Cy),
1.70-1.82 (m, 8 H, Cy), 1.93-2.03 (m, 4 H, Cy), 2.16-2.27 (m, 4 H, Cy),
2.41-2.52 (m, 4 H, Cy), 4.13 (d, 3JHH = 5.6 Hz, 4 H, CH2NH), 4.30 (vt, J′ =
1.8 Hz, 4 H, fc), 4.35 (vt, J′ = 1.8 Hz, 4 H, fc), 4.55 (vt, J′ = 1.7 Hz, 4 H,
fc), 4.62 (m, 4 H, fc), 7.10 (br s, 4 H, NH2 of guanidinium), 7.52 (br s, 4 H,
3
NH2 of guanidinium), 7.84 (t, JHH = 5.4 Hz, 2 H, CH2NH) ppm. 13C{1H}
NMR (100.58 MHz, DMSO-d6): δ = 25.90 (s, Cy), 26.80 (two vt, 2× Cy),
28.44 (s, Cy), 29.55 (s, Cy), 35.86 (vt, J′ = 12 Hz, Cy), 69.38 (s, CH of fc),
70.62 (s, CH of fc), 71.26 (s, CH of fc), 74.15 (vt, J′ = 5 Hz, CH of fc),
74.29 (vt, J′ = 19 Hz, Cipso–P of fc), 84.46 (s, Cipso–CH2 of fc), 156.63 (s,
Cipso of guanidinium), 188.78 (dt, 1JRhC = 74 Hz, 2JPC = 16 Hz, C≡O) ppm.
The signal due to the methylene spacer overlaps with the solvent
1
resonance. 31P{1H} NMR (161.90 MHz, DMSO-d6): δ = 29.8 (d, JRhP
=
122 Hz, PCy2) ppm. FTIR (Nujol): νmax 3326 m, 3158 m, 1946 s, 1939 sh,
1665 s, 1645 s, 1342 w, 1328 w, 1306 w, 1291 w, 1266 w, 1195 w, 1172
w, 1162 m, 1034 m, 1007 w, 854 w, 848 w, 825 m, 747 m, 625 w, 578 m,
481 m, 467 m cm–1. MS (ESI+): m/z 346 ([M – 3Cl]3+), 519 ([M – 2Cl –
HCl]2+), 1037 ([M – Cl –2HCl]+), 1073 ([M – Cl – HCl]+). Anal. Calc. for
C49H74Cl3Fe2N6OP2Rh·H2O (1164.1): C 50.56, H 6.58, N 7.22%. Found
C 50.31, H 6.42, N 6.99%.
Pd-catalysed cross-coupling of aryl bromides with boronic acids. In
a typical run, a dry Schlenk flask was charged with the appropriate aryl
bromide (1.0 mmol), boronic acid (1.1 mmol), sodium carbonate (1.0
mmol) and a ligand (1.1 µmol). An argon atmosphere was established
and the flask was sealed with a septum. Deuterated benzene (1.8 mL),
deaerated water (2.0 mL) and, finally, 5 mM solution of palladium(II)
acetate in deuterated benzene (0.2 mL, 1.0 µmol) were added. The
resulting mixture was vigorously stirred at 50°C for 60 minutes. After
cooling to room temperature, the mixture was diluted with water (5 mL) to
dissolve the crystallizing ionic components and (trifluoromethyl)benzene
(146.1 mg, 1.0 mmol) was added as an internal standard. The benzene
phase was filtered as described above and analysed by 19F NMR
spectroscopy to determine the conversion. Characterisation data of the
coupling products are available in Supporting Information.
Analytical data for 4c. Yellow solid. 1H NMR (399.95 MHz, DMSO-d6): δ
= 4.05 (d, 3JHH = 5.7 Hz, 4 H, CH2NH), 4.38 (vt, J′ = 1.7 Hz, 4 H, fc), 4.40
(vt, J′ = 1.7 Hz, 4 H, fc), 4.44 (s, 4 H, fc), 4.62 (vt, J′ = 1.7 Hz, 4 H, fc),
7.44-7.52 (m, 12 H, Ph), 7.56-7.64 (m, 8 H, Ph), 7.87 (s, 2 H, CH2NH).
13C{1H} NMR (100.58 MHz, DMSO-d6): δ = 69.48 (s, CH of fc), 70.92 (s,
CH of fc), 72.60 (vt, J′ = 2 Hz, CH of fc), 74.33 (vt, J′ = 26 Hz, Cipso–P of
fc), 74.64 (vt, J′ = 6 Hz, CH of fc), 84.96 (s, Cipso–CH2 of fc), 128.08 (vt, J′
= 5 Hz, CH of Ph), 130.17 (s, CH of Ph), 133.37 (vt, J′ = 13 Hz, CH of Ph),
134.34 (vt, J′ = 23 Hz, Cipso of Ph), 156.66 (s, Cipso of guanidinium),
187.18 (dt, 1JRhC = 74 Hz, 2JPC = 16 Hz, C≡O) ppm. The signal due to the
methylene linker overlaps with the solvent resonance. 31P{1H} NMR
Hydroformylation experiments. These experiments were performed in
in a 50mL stainless steel autoclave equipped with a manometer, a
thermostat, a magnetic stirrer and a gas inlet/outlet system. The catalyst
was placed in the autoclave and, subsequently, 1-hexene and dimethyl
sulfoxide (0.75 mL each) were added under nitrogen atmosphere. The
autoclave was closed, flushed three times with hydrogen (5 bar) and,
finally, pressurized with syngas (H2/CO = 1:1) to 10 bar and heated to
80oC for 5 h. When the reaction was finished, the autoclave was cooled
to ambient temperature and depressurised. The organic phase was
separated from the solid residue by vacuum transfer and analysed by GC
(Hewlett-Packard 5890 II) and GC-MS (Hewlett-Packard 5971A).
1
(161.90 MHz, DMSO-d6): δ = 22.6 (d, JRhP = 126 Hz, PPh2) ppm. FTIR
(Nujol): νmax 3316 m, 3141 s, 1970 s, 1647 s, 1435 s, 1339 w, 1306 w,
1164 m, 1097 m, 1071 w, 1028 m, 833 m, 746 m, 695 s, 627 w, 572 m,
535 m, 515 m, 496 s, 471 m cm–1. MS (ESI+): m/z 507 ([M – 2Cl –
HCl]2+), 525 ([M – 2Cl]2+). Anal. Calcd. for C49H50Cl3Fe2N6OP2Rh·¼
Me2CO·H2O (1154.4): C 51.76, H 4.67, N 7.28%. Found C 51.63, H 4.64,
N 6.73%.
Analytical data for 4d. Yellow solid. 1H NMR (399.95 MHz, DMSO-d6): δ
= 4.10 (d, 3JHH = 5.3 Hz, 4 H, CH2NH), 4.33 (s, 4 H, fc), 4.38 (s, 4 H, fc),
4.65 (s, 4 H, fc), 4.69 (s, 4 H, fc), 6.63 (s, 4 H, Fur), 6.90 (d, J = 3 Hz, 4 H,
X-Ray crystallography. Full-sphere diffraction data (θmax = 26° for 3a,
and 27.5° for 3d; completeness > 99%) were recorded using a Nonius
Kappa CCD diffractometer equipped with a Bruker Apex II detector (3d),
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