Organometallics
Article
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298 K, C6D6): δ 1.37 (d, JH,H = 6.84 Hz, 12H, iPr-CH3), 1.50 (m,
4H, COD-CH2), 1.69 (d, 3JH,H = 6.84 Hz, 12H, iPr-CH3), 2.26−2.28
4.12 (m, 2H, COD-CH), 4.34 (s, 5H, Cp), 4.45 (dd, JH,H = 2.3 Hz,
4JH,H = 0.8 Hz, 1H, subst. Cp-CH), 6.03 (br s, 1H, NH), 6.93−7.25
(m, 6H, Dipp-CH). 13C NMR (100.6 MHz, 298 K, C6D6): δ 23.2
(iPr-CH3), 23.6 (iPr-CH3), 24.3 (iPr-CH3), 24.8 (iPr-CH3), 25.5
(iPr-CH3), 26.2 (iPr-CH3), 27.0 (iPr-CH3), 28.1 (4C, iPr-CH), 28.4
(4C, iPr-CH), 28.6 (iPr-CH3), 30.8 (COD-CH2), 32.5 (COD-CH2),
33.3 (COD-CH2), 33.5 (COD-CH2), 53.7 (2C, COD-CH), 54.5
(2C, COD-CH), 69.5 (5C + 1C, Cp-CH + subst Cp-CH), 72.2
(subst. Cp-CH), 73.9 (iPr-CH), 74.7 (subst. Cp-CH), 76.7 (iPr-CH),
88.5 (ipso-Cp), 103.4 (Cp-C-Ir), 123.4 (Dipp-CH), 124.4 (Dipp-
CH), 124.6 (Dipp-CH), 125.3 (Dipp-CH), 127.1 (Dipp-CH), 127.9
(Dipp-CH), 129.4 (q-Dipp-C), 133.1 (q-Dipp-C), 143.8 (q-Dipp-C),
144.4 (q-Dipp-C), 146.9 (q-Dipp-CH), 148.3 (q-Dipp-CH), 176.5
(NCN). IR (ATR, ν, cm−1): 1341 (w, νC−H), 1362 (w, νC−H), 1383
(w, νC−H), 1435 (w, νC−H), 1474 (m, νC−H), 1543 (s, νC−Car), 1589
(w, νC−Car), 1638 (w, νCN), 2822 (m, νC−H), 2867 (m, νC−H), 2958
(m, νC−H), 3079 (w, νC−H), 3355 (m, νN−H). Elemental analysis
(calcd for C43H55FeIrN2) [%]: C, 59.98 (60.91); H, 6.35 (6.54); N,
2.93 (3.30) (carbon values were reproducibly to low because of metal
carbide formation).
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(m, 4H, COD-CH2), 3.49 (pseudot, JH,H = 1.98 Hz, 2H, subst. Cp-
CH), 3.62 (br, 4H, COD-CH), 3.74 (pseudot, JH,H = 1.98 Hz, 2H,
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subst. Cp-CH), 3.91 (s, 5H, Cp), 4.07 (sept., 3JH,H = 6.84 Hz, 4H, iPr-
CH), 7.12−7.21 (m, 6H, Dipp-CH). 13C{1H} NMR (75 MHz, 298 K,
C6D6): δ 24.5 (2C, iPr-CH3), 25.0 (2C, iPr-CH3), 28.8 (4C, iPr-CH),
30.7 (4C, COD-CH2), 68.9 (2C, subst. Cp-CH), 69.8 (5C, Cp), 70.4
(2C, subst. Cp-CH), 78.2 (d, JC,Rh = 2.6 Hz, ipso-Cp-C), 78.9 (d, JR,hC
= 12.7 Hz, 4C, COD-CH), 123.8 (2C, meta-Dipp-CH), 124.7 (para-
Dipp-CH), 143.3 (4C, ortho-DippC-iPr), 144.2 (2C, ipso-DippC),
177.6 (d, JC,Rh = 5.2 Hz, NCN). IR (ATR, ν, cm−1): 1381 (w, νC−H),
1448 (s, νC−H), 1498 (w, νC−H), 1551 (w, νC−Car), 1636 (w, νCN),
2830 (m, νC−H), 2867 (m, νC−H), 2954 (m, νC−H), 3058 (m, νC−H),
3361 (w, νN−H decomposition). Elemental analysis (calcd for
C43H55FeN2Rh) [%]: C, 68.17 (68.08); H, 7.22 (7.31); N, 3.31
(3.69).
[fc{C(NMes)2Rh(cod)}2] (5): 278 mg of 3 (0.286 mmol) and 141
mg of [Rh(cod)Cl]2 (0.286 mmol) were stirred in 23 mL of THF
overnight. The obtained orange suspension was evacuated to dryness.
The solid was mixed with 20 mL of toluene and heated to 110 °C.
The hot mixture was quickly filtered into a Schlenk tube using a
syringe filter within a glovebox. The solution was layered with 40 mL
of Et2O and stored for several weeks. The obtained red crystals were
filtered off, washed with a small amount of Et2O, and dried in vacuo.
[CpFe(C5H3){C(NHDipp)(NDipp)Rh(CO)2}] (8): 50 mg of 5
(0.066 mmol) was mixed with 10 mL of dichloromethane within a
Schlenk tube. After three freeze−pump−thaw cycles, 1.5 bar CO was
applied and stirred at room temperature. The solid completely
dissolves during that process. After 1 h, CO was applied a second
time. After stirring overnight, the mixture was dried in vacuo and
brought back in solution in 3 mL of toluene. The solution was filtered
into a thin Schlenk tube, using a syringe filter. Crystals were obtained
after hot recrystallization from toluene in 47% yield (22 mg, 0.031
mmol). Analytical data for [Fc{C(NHDipp)(NDipp)Rh(CO)2}] (8)
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Yield: 256 mg (0.220 mmol, 77%). H NMR (400.1 MHz, 298 K,
C6D6): δ 1.52 (m, 8H, COD-CH2), 2.23 (br, 8H, COD-CH2), 2.31
(s, 12H, para-CH3), 2.48 (s, 24H, ortho-CH3), 3.53 (br, 8H, COD-
CH), 3.76 (pseudot, JH,H = 2.0 Hz, 4H, cp-CH), 4.01 (pseudot, JH,H = 2.0
Hz, 4H, cp-CH), 6.89 (s, 8H, mesityl-CH). 13C NMR (100.6 MHz,
298 K, C6D6): δ 19.3 (8C, ortho-CH3), 21.2 (4C, para-CH3), 31.3
(8C, COD-CH2), 69.8 (4C, cp-CH), 73.3 (4C, cp-CH), 76.4 (2C, cp-
CCN2), 78.7 (d, JC,Rh = 12.5 Hz, 4C, COD-CH), 128.6 (8C, meta-
CH), 128.7 (4C, para-CCH3), 132.6 (4C, ipso-C), 143.0 (8C, ortho-
CCH3), NCN-carbon could not be detected. IR (ATR, ν, cm−1):
1407 (m, νC−H), 1430 (s, νC−H), 1451 (s, νC−H), 1473 (s, νC−H), 1506
(w, νC−Car), 2724 (w, νC−H), 2829 (w, νC−H), 2877 (w, νC−H), 2913
(w, νC−H), 2969 (w, νC−H), 2989 (w, νC−H). Elemental analysis (calcd
for C64H76FeN4Rh2) [%]: C, 66.23 (66.10); H, 6.19 (6.59); N, 4.75
(4.82).
are as follows: 1H NMR (400.1 MHz, 298 K, C6D6): δ 0.70 (d, 3JH,H
=
6.8 Hz, 3H, iPr-CH3), 0.89 (d, 3JH,H = 6.8 Hz, 3H, iPr-CH3), 0.94 (d,
3JH,H = 6.8 Hz, 3H, iPr-CH3), 1.12 (d, JH,H = 6.9 Hz, 3H, iPr-CH3),
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1.14 (d, 3JH,H = 7.0 Hz, 3H, iPr-CH3), 1.21 (d, 3JH,H = 7.0 Hz, 3H, iPr-
CH3), 1.37 (d, 3JH,H = 7.0 Hz, 3H, iPr-CH3), 1.67 (d, 3JH,H = 6.7 Hz,
3H, iPr-CH3), 3.00 (dd, 3JH,H = 2.5 Hz, 4JH,H = 0.9 Hz, 1H, subst. Cp-
CH), 3.04 (sept., 3JH,H = 6.8 Hz, 1H, iPr-CH), 3.26 (sept., 3JH,H = 6.9
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Hz, 1H, iPr-CH), 3.38 (sept., JH,H = 6.8 Hz, 1H, iPr-CH), 3.62
(sept., 3JH,H = 6.8 Hz, 1H, iPr-CH), 3.80 (t, 3JH,H = 1.9 Hz, 1H, subst.
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Cp-CH), 4.11 (t, JH,H = 1.9 Hz, 1H, subst. Cp-CH), 4.32 (s, 5H,
Cp), 5.92 (br s, 1H, NH), 6.94−7.36 (m, 6H, Dipp-CH). The 13C
NMR spectrum was not detectable because of the low concentration
of compound 8 in solution. As described above, the ratio of 8/8′ is
about 1:3 in solution, together with the low solubility, making it
impossible to get sufficient. IR (ATR, ν, cm−1): 1361 (w, νC−H), 1384
(w, νC−H), 1442 (m, νC−H), 1549 (w, νC−Car), 1633 (w, νC−N), 1990
(s, νCO), 2060 (s, νCO), 2867 (w, νC−H), 2924 (m, νC−H), 2960
(m, νC−H), 3352 (w, νN−H). Elemental analysis (calcd for
C37H43FeN2O2Rh with half a molecule CH2Cl2 per product
molecule) [%]: C, 59.71 (60.14); H, 5.60 (5.92); N, 3.74 (3.74).
Analytical data for [Fc{C(NDipp)2Rh(CO)2}] (8′): 1H NMR (400.1
MHZ, 298 K, C6D6): δ 1.32 (d, 3JH,H = 6.96 Hz, 12H, iPr-CH3), 1.57
(d, 3JH,H = 6.76 Hz, 12H, iPr-CH3), 3.49 (pseudot, 3JH,H = 2.02 Hz, 2H,
subst. Cp-CH), 3.68 (pseudot, 3JH,H = 2.00 Hz, 2H, subst. Cp-CH), 3.91
(s, 5H, Cp), 3.97 (sept., 3JH,H = 6.88 Hz, 4H, iPr-CH), 6.94−7.36 (m,
6H, Dipp-CH). 13C NMR (100.6 MHz, 298 K, C6D6): δ 23.2 (2C,
iPr-CH3), 24.4 (2C, iPr-CH3), 29.0 (4C, iPr-CH), 69.4 (2C, subst.
Cp-CH), 69.6 (5C, Cp), 70.0 (2C, subst. Cp-CH), 75.1 (d, JC,Rh = 2.5
Hz, ipso-Cp-C), 123.8 (4C, meta-Dipp-CH), 126.4 (2C, para-Dipp-
CH), 143.7 (4C, ortho-DippC-iPr), 145.1 (2C, ipso-DippC), 186.7 (d,
JC,Rh = 69.6 Hz, 2C, CO), NCN was not detected.
[Fe{(C5H3)(C(NHMes)(NMes)Rh(CO)2)}2] (9): 150 mg of 7
(0.129 mmol) was mixed with 20 mL of dichloromethane within a
Schlenk tube. After three freeze−pump−thaw cycles, 1.5 bar CO was
applied and stirred at room temperature. The solid completely
dissolves during that process. After 1 h, CO was applied a second
time. After stirring overnight, the mixture was dried in vacuo and
brought back in solution in 3 mL of benzene. The solution was
filtered into a thin Schlenk tube, using a syringe filter. Upon storage
for 3 weeks, the solution turned brown and red crystals precipitated
[fc{C(NMes)2Ir(cod)}2] (6): 100 mg of 3 (0.286 mmol) and 141
mg [Ir(cod)Cl]2 (0.286 mmol) were stirred in THF overnight. The
obtained orange suspension was evacuated to dryness. The solid was
mixed with 20 mL of toluene and heated to 110 °C and quickly
filtered into a Schlenk tube. Crystals were obtained after storage
overnight. Yield: 73 mg (0.220 mmol, 77%).
Because of insolubility, no sufficient NMR data could be collected
in any common solvent. IR (ATR, ν, cm−1): 1346 (w, νC−H), 1374
(m, νC−H), 1449 (s, νC−H), 1476 (s, νC−H), 1514 (w, νC−Car), 1547 (s,
νC−Car), 1608 (w, νC−Car), 1631 (w, νCN), 2827 (s, νC−H), 2866 (s,
νC−H), 2917 (s, νC−H), 3342 (w, νN−H decomposition). Elemental
analysis (calcd for C64H76FeIr2N4) [%]: C, 57.73 (57.30); H, 5.70
(5.71); N, 3.75 (4.18).
[CpFe(C5H3){C(NHDipp)(NDipp)Ir(cod)}] (7): 100 mg of 2
(0.124 mmol) and 42 mg of [Ir(cod)Cl]2 (0.062 mmol) were stirred
in 15 mL of THF overnight. The obtained orange suspension was
evacuated to dryness. The solid was mixed with 20 mL of toluene and
filtered. The solvent was evacuated again, and the residue was
suspended in n-heptane. Hot recrystallization led to the product in
52% yield (55 mg, 0.065 mmol). 1H NMR (400.1 MHz, 298 K,
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C6D6): δ 0.68 (d, JH,H = 6.5 Hz, 3H, iPr-CH3), 0.83 (d, JH,H = 6.5
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Hz, 3H, iPr-CH3), 0.93 (d, JH,H = 6.5 Hz, 3H, iPr-CH3), 1.16 (d,
3JH,H = 6.5 Hz, 3H, iPr-CH3), 1.38 (d, JH,H = 6.5 Hz, 3H, iPr-CH3),
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1.36 (d, 3JH,H = 6.5 Hz, 3H, iPr-CH3), 1.62 (d, 3JH,H = 6.5 Hz, 3H, iPr-
3
CH3), 1.75 (d, JH,H = 6.5 Hz, 3H, iPr-CH3), 1.79−1.87 (m, 4H,
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COD-CH2), 2.23−2.38 (m, 4H, COD-CH2), 2.96 (dd, JH,H = 2.5
Hz, 4JH3,H = 0.8 Hz, 1H, subst. Cp-CH), 3.07 (m, 2H, COD-CH), 3.32
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(sept., JH,H = 6.8 Hz, 1H, iPr-CH), 3.39 (sept., JH,H = 6.8 Hz, 1H,
iPr-CH), 3.63 (sept., 3JH,H = 6.8 Hz, 1H, iPr-CH), 3.77 (sept., 3JH,H
=
6.8 Hz, 1H, iPr-CH), 4.09 (tpseudo, 3JH,H = 2.3 Hz, 1H, subst. Cp-CH),
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Organometallics XXXX, XXX, XXX−XXX