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(m), 1431 (w), 1473 (s), 1603 (m), 1632 (vs), 2729 (vw), 2853 (vw),
(p-Ar-C), 125.5 (m-Ar-C), 140.7 (o-Ar-Cipso), 144.4 ppm (Ar-Cipso-N). IR
2914 (vw), 2943 (vw), 2995 (vw) cm–1. Elemental analysis (calcd.) (ATR, ν): ν = 429 (w), 783 (s), 1097 (w), 1253 (w), 1322 (w), 1471 (vs),
˜ ˜
[%]: C: 81.69 (81.68), H: 7.81 (8.30), N: 9.79 (10.03).
2103 (vw), 2865 (vw), 2957 (w), 3255 (vw) cm–1. EI/MS: m/z (%) =
598.31 (24.46) [M]+. m.p. 175 °C (dec); No satisfactory elemental
analysis could be obtained, due to the limited stability of 3.
Rhodium(I) Complexes
1: 200 mg of L1Li (2 equiv., 0.536 mmol) and 132 mg [Rh(cod)Cl]2
(1 equiv., 0.267 mmol) were added to a Schlenk tube dissolved in
15 mL of THF and stirred for two days. The mixture was evacuated
to dryness and the residual solid extracted with 8 mL of toluene. For
the separation of the LiCl the yellow mixture was filtered through
a syringe filter within a glovebox and reduced to dryness. The re-
sulting yellow solid was recrystallized from 5 mL of hexane within
4: A solution of 100 mg L4Na (1 equiv., 0.107 mmol) in 8 mL THF
was added dropwise to a solution of 53 mg [Rh(cod)Cl]2 (1 equiv.,
0.107 mmol) in 12 mL THF in an ice bath. After stirring overnight,
the reddish-brown suspension was evacuated to dryness and ex-
tracted with 5 mL toluene. The mixture was filtered into a thin
Schlenk tube and reduced to approximately 3 mL. The solution was
layered with 9 mL Et2O and stored in the fridge (–35 °C) for several
months. 6 slowly precipitates in form of red crystals containing one
molecule Et2O per formula unit. The crystals were washed with Et2O
and dried in vacuo. Yield: 38 mg (0.0324 mmol, 30 %). 1H NMR
1
a closed flask at 100 °C. Yield: 148 mg (0.293 mmol, 55 %). H NMR
(400.1 MHz, 298 K, C6D6): δ = 1.06 (s, 3 H, N2CCH3), 1.51 (m, 4 H,
COD CH2), 2.18 (s, 6H para CH3), 2.27 (m, 4 H, COD CH2), 2.52 (s, 12
H, ortho CH3), 3.76 (s, 4 H, COD CH), 6.84 (m, 4 H, mesityl CH) ppm.
13C NMR (100.6 MHz, 298 K, C6D6): δ = 15.2 (d, JCRh = 1.7 Hz, 1 C,
N2CCH3), 18.9 (s, 4 C, ortho CH3), 21.0 (s, 2 C, para CH3), 31.4 (s, 4 C,
COD CH2), 77.8 (d, JCRh = 12.8 Hz, 4 C, COD CH), 129.0 (s, 4 C, mesityl
CH), 133.1 (s, 2 C, ipso C), 133.6 (s, 4 C, ortho CCH3), 141.6 (s, 2 C,
3
(400.1 MHz, 298 K, C6D6): δ = 1.03 (d, J = 6.9 Hz, 24 H, Dipp CH3),
3
1.33 (m, 8 H, COD CH2), 1.52 (d, J = 6.9 Hz, 24 H, Dipp CH3), 2.09
3
(m, 8 H, COD CH2), 3.42 (br., 8 H, COD CH), 3.67 [sept, J = 6.8 Hz,
8 H, Dipp HC(CH3)2], 7.01 (m, 12 H, Dipp Ar-CH) ppm. 13C NMR
(100.6 MHz, 298 K, C6D6): δ = 23.4 (s, 8 C, CH3), 25.3 (s, 8 C, Dipp
CH3), 28.9 [s, 8 C, Dipp CH(CH3)2], 30.6 (s, 8 C, COD CH2), 80.0 (d,
1JCRh = 12.7 Hz, COD CH), 81.6 (d, JCRh = 3.0 Hz, 2 C, alkene CC),
123.3 (s, 8 C, meta CH), 125.3 (s, 4 C, para CH), 140.5 (s, 4 C, ipso
C), 143.4 (s, 8 C, CCH3), 159.0 (d, JCRh = 5.6 Hz, CN2) ppm. IR (ATR,
para CCH3), 179.1 (d, JCRh = 5.4 Hz, 1 C, N2C) ppm. IR (ATR, ν): ν =
˜ ˜
466 (m), 480 (m), 501 (w), 517 (w), 535 (w), 560 (m), 633 (vw), 692
(vw), 721 (vw), 745 (vw), 768 (vw), 784 (vw), 811 (vw), 857 (vs), 884
(vw), 948 (w), 981 (m), 1033 (w), 1150 (s), 1222 (vs), 1260 (vs), 1301
(w), 1356 (w), 1374 (w), 1428 (m), 1475 (s), 2728 (vw), 2827 (vw),
2872 (vw), 2916 (vw), 2936 (vw), 2964 (vw), 2991 (vw) cm–1. Elemen-
tal analysis (calcd.) [%]: C: 66.74 (66.66), H: 7.20 (7.39), N: 5.53 (5.55).
ν): ν = 401 (m), 423 (m), 445 (m), 482 (w), 529 (w), 581 (vw), 662
˜ ˜
(w), 689 (vw), 746 (s), 791 (s), 805 (w), 817 (vw), 864 (w), 879 (w),
937 (vw), 955 (w), 1000 (w), 1042 (vw), 1060 (vw), 1075 (vw), 1097
(w), 1112 (w), 1159 (vw), 1178 (w), 1222 (m), 1264 (m), 1324 (m),
1361 (m), 1381 (w), 1420 (m), 1464 (vs), 2831 (vw), 2868 (w), 2927
(w), 2956 (w), 3057 (vw) cm–1. Elemental analysis (calcd.) [%]: C:
69.54 (69.73), H: 7.52 (7.92), N: 4.72 (4.78).
2: 200 mg L2Na (1.0 equiv., 0.439 mmol) were added to 107 mg
[Rh(cod)Cl]2 (0.5 equiv., 0.217 mmol) and dissolved in 15 mL of THF.
The mixture was stirred for 12 h and reduced to dryness. The resi-
due was extracted with 8 mL of toluene and filtered through a
syringe filter within a glovebox. The solution was reduced to half
of its volume and stored at –35 °C. After two days the resulting
crystals were separated using a syringe, washed with a small
amount of cold hexane and dried in vacuo. Yield: 90 mg
5: A mixture of 200 mg L5Na (1 equiv., 0.243 mmol) and 120 mg
[Rh(cod)Cl]2 (1 equiv., 0.243 mmol) in 20 mL of THF was stirred in
an ice bath. The compounds slowly dissolve, whilst an orange solid
precipitates. After stirring overnight, the mixture was dried in vacuo
and 25 mL of toluene were added. The red suspension was filtered
through a syringe filter into a thin Schlenk tube and the solvent
was reduced, until the formation of precipitate. The mixture was
heated, until everything was fully dissolved and layered with 40 mL
of hexane. After diffusion the obtained orange red crystals were
filtered off, washed with hexane and dried in vacuo (189 mg,
1
(0.153 mmol, 35 %). H NMR (400.1 MHz, 298 K, C6D6): δ = 1.21 (s,
3 H, N2CCH3), 1.31 (d, 3J = 6.9 Hz, 12 H, Dipp CH3), 1.48 (d, 3J =
6.9 Hz, 12 H, Dipp CH3), 1.52 (m, 4 H, COD CH2), 2.30 (m, 4 H, COD
3
CH2), 3.78 (br., 4 H, COD CH), 4.04 [sept, J = 6.9 Hz, CH(CH3)2], 7.11
(s, 6 H, Dipp CH) ppm. 13C NMR (100.6 MHz 298 K, C6D6): δ = 16.3
(d, JCRh = 1.7 Hz, 1 C, N2CCH3), 24.3 (s, 4 C, Dipp CH3), 24.7 (s, 4 C,
Dipp CH3), 28.3 [s, 4 C, Dipp CH(CH3)2], 31.1 (s, 4 C, COD CH2), 78.2
(d, JCRh = 12.8 Hz, 4 C, Dipp CH), 123.5 (s, 4 C, Dipp CH), 125.3 (s, 2
C, Dipp CH), 141.0 (s, 2 C, Dipp ipso C), 180.2 (d, JCRh = 5.3 Hz, N2C)
1
0.164 mmol, 68 %). H NMR (400.1 MHz, 298 K, C6D6): δ = 1.44 (m,
8 H, COD CH2), 2.08 (s, 12 H, para CH3), 2.15 (br., 8 H, COD CH2),
2.32 (s, 24 H, ortho CH3), 3.74 (br., 8 H, COD CH), 6.61 (s, 8 H, mesityl
CH), 6.84 (s, 4 H, phenyl CH) ppm. 13C NMR (100.6 MHz, 298 K,
C6D6): δ = 19.1 (s, 8 C, ortho CH3), 21.0 (s, 4 C, para CH3), 31.2 (s, 8
C, COD CH2), 78.7 (d, JCRh = 12.7 Hz, COD CH), 126.8 (s, 2 C, phenyl
CCN2), 128.7 (s, 4 C, phenyl CHCCN2), 129.1 (s, 8 C, mesityl CH),
132.5 (s, 4 C, para CCH3), 132.6 (s, 4 C, mesityl ipso C), 141.7 (s, 8 C,
ppm. IR (ATR, ν): ν = 413 (w), 442 (m), 482 (w), 491 (w), 521 (w), 540
˜ ˜
(m), 587 (vw), 685 (w), 719 (w), 747 (vs), 765 (s), 789 (vs), 802 (w),
816 (vw), 848 (w), 868 (w), 933 (w), 954 (w), 978 (w), 991 (w), 1045
(vw), 1057 (w), 1077 (vw), 1098 (w), 1153 (w), 1175 (w), 1193 (w),
1218 (m), 1245 (m), 1263 (vs), 1320 (s), 1340 (w), 1362 (vs), 1381
(m), 1430 (vs), 1443 (s), 1460 (vs), 1481 (s), 2830 (w), 2867 (w), 2919
(w), 2956 (m), 2999 (vw), 3056 (vw) cm–1. Elemental analysis (calcd.)
[%]: C: 69.62 (69.37), H: 8.02 (8.39), N: 4.73 (4.76).
ortho CCH3), 178.2 (d, JCRh = 5.1 Hz, CN2) ppm. IR (ATR, ν): ν = 457
˜ ˜
(vw), 482 (w), 499 (w), 542 (w), 575 (s), 646 (w), 671 (w), 741 (w),
782 (w), 814 (w), 846 (s), 885 (vw), 950 (w), 964 (m), 990 (w), 1005
(w), 1031 (w), 1076 (vw), 1117 (w), 1147 (w), 1173 (w), 1207 (s), 1268
(m), 1301 (w), 1326 (w), 1371 (m), 1385 (m), 1430 (s), 1475 (vs), 1568
(vw), 1719 (vw), 2726 (vw), 2831 (vw), 2876 (vw), 2914 (w), 3001
(vw) cm–1. Elemental analysis (calcd.) [%]: C: 68.37 (68.30), H: 6.60
(6.88), N: 5.16 (5.31).
3: A solution of [Rh(cod)Cl]2 (25.0 mg, 0.05 mmol) in toluene (3 mL)
was added dropwise to a solution of L3Na (49.0 mg, 0.10 mmol) at
–30 °C and then stirred at room temperature for 1 h. After filtration,
the red solution was kept at –30 °C, whereupon 3 was obtained as
yellow crystals. Yield: 22 mg (37 %). 1H NMR (300 MHz, 298 K, C6D6):
3
3
δ = 1.47 [d, JHH = 6.86 Hz, 12 H, CH(CH3)2], 1.50 [d, JHH = 6.86 Hz,
12 H, CH(CH3)2], 1.50 (m, 4 H, COD-CH2), 1.68 (s, 1 H, C≡CH) 2.25 (br.,
6: 150 mg L6Na (1 equiv., 0.175 mmol) and 86 mg [Rh(cod)Cl]2
(1 equiv., 0.175 mmol) were weighed into a Schlenk tube and stirred
in 10 mL of THF overnight. The orange reaction mixture was evacu-
3
4 H, COD-CH2), 3.82 (br., 4 H, COD-CH), 4.09 [sept, JHH = 6.89 Hz, 4
H, CH(CH3)2], 6.99–7.12 ppm (m, 6 H, Ar-H). 13C NMR (75 MHz, 298 K,
C6D6): δ = 24.7 [CH(CH3)2], 24.9 [CH(CH3)2], 28.8 [CH(CH3)2] 30.9 ated to dryness. The resulting reaction mixture was extracted with
1
(COD-CH2), 79.0 (d, JRhC = 13.02 Hz; COD-CH), 82.6 (C≡CH), 123.1
10 mL of hot toluene and separated using a syringe filter. After
Eur. J. Inorg. Chem. 0000, 0–0
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