B. F. Straub, M. Wrede, K. Schmid, F. Rominger
SHORT COMMUNICATION
= 2.4 Hz, 4 H, Ar-H), 7.33 (d, JH,H = 2.2 Hz, 4 H, Ar-H), 1.56 (s, 1.10–1.50 (m, 72 H, CMe3) ppm. 13C{1H} NMR (75.47 MHz,
36 H, CMe3), 1.36 (s, 36 H, CMe3) ppm. H NMR (250.13 MHz, CDCl3, 25 °C): δ = 157.4 (N=CH-N), 156.1 (CAr), 141.1 (CAr),
4
1
4
CDCl3, 25 °C): δ = 7.26 (d, JH,H = 2.0 Hz, 4 H, Ar-H), 7.05 (d,
138.6 (CAr), 138.3 (CAr), 134.8 (CAr), 132.6 (CAr), 130.7 (CAr),
4JH,H = 1.7 Hz, 4 H, Ar-H), 1.31 (s, 36 H, CMe3), 1.26 (s, 36 H, 129.9 (CAr), 128.3 (CAr), 125.7 (CAr), 125.2 (CAr), 122.1 (CAr), 52.0,
CMe3) ppm. 13C{1H} NMR (75.46 MHz, CDCl3/[D6]DMSO,
25 °C): δ = 149.9 (CAr), 143.3 (CAr), 138.4 (CAr), 132.6 (CAr), 126.2
(CAr), 124.4 (CAr), 35.5 (CMe3), 34.7 (CMe3), 34.4 (Me), 32.3 (Me)
35.5, 34.5, 32.3 (Me), 32.1 (Me), 30.8, 30.1, 21.4, 18.1, 15.7 ppm.
HRMS (ESI–) m/z (%) 843.58778 (100), 844.59124 (60),
845.59550 (16) [M]– (ESI+) m/z (%) = 307.21708 (100), 308.22045
=
ppm. Mp Ͼ 305 °C. IR (KBr): ν = 3452, 2960, 2906, 2870, 1465,
(25); Mp Ͼ300 °C. IR (KBr): ν = 3436, 2952, 2905, 2868, 1632,
˜
˜
1433, 1405, 1389, 1361, 1282, 1243, 1201, 1100, 877, 849, 802, 783,
768, 682, 682, 607 cm–1. C76H120AlNaO9 (1227.73): calcd. C 74.35,
H 9.85; found C 74.18, H 9.52. MS (ESI–): m/z (%) = 834.71 (100),
844.61 (60), 845.70 (19) [M – Na]–.
1463, 1431, 1404, 1387, 1359, 1281, 1242, 1200, 1100, 873, 803,
783, 769, 683, 607 cm–1. C81H117AlN2O5 (1225.79): calcd. C 79.37,
H 9.62, N 2.29; found C 79.20, H 9.67, N 2.18. X-ray: a single-
crystal was obtained from Et2O.
Sodium Mono(tetrahydrofuran) Altebate: This compound was ob-
tained by thf elimination at 120 °C and 1 mbar over a period of
four days, whereby the solubility of the sodium altebate salt de-
creases. After thf elimination, a colorless product was obtained.
Yield: 4.60 g (0.49 mmol, 96%). 1H NMR (300.13 MHz, [D6]-
Tetrabutylammonium Altebate: A round-bottomed flask was
charged with lithium bis(3,5,3Ј,5Ј-tetra-tert-butyl-2,2Ј-diphenolato)-
aluminate(III) (thf)4 adduct (2.00 g, 1.80 mmol) dissolved in
CH2Cl2 (10 mL). A solution of tetrabutylammonium bromide
(1.00 g, 3.10 mmol) in CH2Cl2 (10 mL) was added. A colorless pre-
cipitate (LiBr) was formed. The suspension was filtered through
Celite and washed with CH2Cl2. After removal of the solvent in
vacuo, the product was extracted with pentane. Evaporation of the
solvent afforded a colorless powder. Yield: 1.05 g (0.97 mmol,
4
acetone, 25 °C): δ = 7.18 (d, JH,H = 3.7 Hz, 4 H, Ar-H), 6.97 (d,
4JH,H = 3.7 Hz, 4 H, Ar-H), 3.64 (m, Ͻ 4 H, thf), 1.80 (m, Ͻ 4 H,
thf), 1.31 (s, 36 H, CMe3), 1.31 (s, 36 H, CMe3) ppm.
13C{1H} NMR (75.47 MHz, [D6]acetone, 25 °C): δ = 156.8 (CAr),
138.7 (CAr), 138.4 (CAr), 133.5 (CAr), 128.4 (CAr), 122.0 (CAr), 68.1 54%). 1H NMR (300.13 MHz, [D6]acetone, 25 °C): δ = 7.17 (d,
4
(thf), 35.8 (CMe3), 34.6 (CMe3), 33.2 (Me), 31.2 (Me) ppm. De-
4JH,H = 2.7 Hz, 4 H, Ar-H), 6.96 (d, JH,H = 2.7 Hz, 4 H, Ar-H),
3
comp. 261 °C. IR (KBr): ν = 3528, 3414, 2961, 2907, 2870, 1644,
3.46 (t, JH,H = 8.4 Hz, 8 H, NCH2), 1.84 (m, 8 H, CH2), 1.45 (m,
˜
3
1464, 1431, 1405, 1389, 1361, 1282, 1242, 1201, 1099, 875, 802,
8 H, CH2), 1.30 (m, 72 H, CMe3), 0.98 (t, JH,H = 8.4 Hz, 12 H,
782, 769, 683, 606 cm–1.
CH3) ppm. 13C{1H} NMR (75.47 MHz, [D6]acetone, 25 °C): δ =
157.2 (CAr), 139.2 (CAr), 138.8 (CAr), 133.9 (CAr), 128.8 (CAr),
122.5 (CAr), 59.8 (NCH2), 36.2, 35.0, 32.7 (Me), 32.4 (Me), 31.6,
1,3-Bis(2,6-diisopropylphenyl)imidazolinium Altebate: Under inert
gas, 1,3-bis(2,6-diisopropylphenyl)imidazolinium chloride (300 mg,
0.701 mmol) was dissolved in CH2Cl2 (20 mL). A solution of lith-
ium bis(3,5,3Ј,5Ј-tetra-tert-butyl-2,2Ј-diphenolato)aluminate(III)·
4thf (825 mg, 0.724 mmol) in CH2Cl2 (20 mL) was added whilst
stirring. A colorless precipitate of LiCl was formed. The suspension
was filtered through Celite and washed with CH2Cl2. Removal of
the solvent gave a colorless product. Yield: 860 mg (0.695 mmol,
24.8, 20.8, 14.3 ppm. Mp 150 °C. IR (KBr): ν = 3424, 2957, 2905,
˜
2874, 1464, 1432, 1405, 1387, 1359, 1283, 1241, 1200, 875, 847,
783, 767, 702, 682, 620, 607 cm–1. C72H116AlNO4 (1086.68): calcd.
C 79.58, H 10.76, N 1.29; found C 79.34, H 10.90, N 1.19. HRMS
(ESI–): m/z (%) = 843.58236 (100), 844.58700 (70), 845.59225 (20)
[M]–; (ESI+): m/z (%) = 242.28395 (100).
1
3
96%). H NMR (300.13 MHz, CDCl3, 25 °C): δ = 7.53 (t, JH,H
=
CCDC-767474 [for lithium tetrakis(tetrahydrofuran)bis(3,3Ј,5,5Ј-
7.8 Hz, 2 H, Ar-H), 7.38 (s, 1 H, N=CH-N), 7.28 (s, 4 H, Ar-H), tetra-tert-butyl-2,2Ј-diphenolato)aluminate(III)], -767475 [for 1,3-
4
4
7.13 (d, JH,H = 2.6 Hz, 4 H, Ar-H), 7.00 (d, JH,H = 2.6 Hz, 4 H,
dimesitylimidazolinium altebate], and -767997 [for 1,3-bis(2,6-di-
isopropylphenyl)imidazolium altebate] contain the supplementary
crystallographic data for this paper. These data can be obtained
3
Ar-H), 3.77 (s, 4 H, CH2), 3.49 (q, Et2O), 3.73 (sept., JH,H
=
6.8 Hz, H, MeCHMe), 1.10–1.50 (m, 96 H, Me) ppm.
4
13C{1H} NMR (75.47 MHz, CDCl3,25 °C): δ = 157.5 (N=CH-N), free of charge from The Cambridge Crystallographic Data Centre
156.2 (CAr), 146.2 (CAr), 138.7 (CAr), 138.2 (CAr), 132.5 (CAr),
132.3 (CAr), 129.2 (CAr), 128.0 (CAr), 125.7 (CAr), 122.1 (CAr), 66.2,
54.1, 35.5, 34.4, 32.2 (Me), 30.8 (Me), 29.5, 25.9, 24.1, 15.7 ppm.
via www.ccdc.cam.ac.uk/data_request/cif.
Supporting Information (see footnote on the first page of this arti-
cle): Additional synthetic protocols, data relevant for yields and
costs of the WCA in Table 1, NMR spectra, additional color fig-
ures, and Cartesian coordinates for DFT calculations.
Mp Ͼ 300 °C. IR (KBr): ν = 3435, 2960, 2870, 1634, 1464, 1431,
˜
1405, 1387, 1359, 1325, 1281, 1243, 1200, 1100, 874, 803, 783, 769,
683, 607 cm–1. C87H129AlN2O5 (1309.95): calcd. C 79.77, H 9.93,
N 2.14; found C 79.55, H 9.86, N 2.01. HRMS (ESI–): m/z (%) =
843.58400 (100), 844.58738 (60), 845.59074 (19) [M]–; (ESI+): m/z
(%) = 391.31072 (100). X-ray: a single crystal was obtained by
crystallization from Et2O.
Acknowledgments
Financial support by the Deutsche Forschungsgemeinschaft
(DFG) and the University of Heidelberg by the FRONTIER pro-
gram is gratefully acknowledged. We thank the Klaus Römer Foun-
dation for financial support, Mr. Thomas Zessin for the exchange
of compounds, and Mrs. Bettina Burk for an internship.
1,3-Dimesitylimidazolinium Altebate–Diethyl Ether: Under inert
gas, 1,3-bis(2,4,6-trimethylphenyl)imidazolinium chloride (300 mg,
0.872 mmol) was dissolved in CH2Cl2 (20 mL). A solution of lith-
ium bis(3,5,3Ј,5Ј-tetra-tert-butyl-2.2Ј-diphenolato)aluminate(III)·
4thf (1.03 g, 0.904 mmol) in CH2Cl2 (20 mL) was added whilst
stirring. A colorless precipitate of LiCl was formed. The suspension
was filtered through Celite and washed with CH2Cl2. Removal of
the solvent in vacuo afforded a colorless solid. Yield: 1.01 g
(0.877 mmol, 97%). 1H NMR (300.13 MHz, CDCl3, 25 °C): δ =
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4
7.44 (s, 1 H, N=CH-N), 7.13 (d, JH,H = 2.6 Hz, 4 H, Ar-H), 6.99
4
(d, JH,H = 2.6 Hz, 4 H, Ar-H), 6.96 (s, 4 H, Ar-H), 3.76 (s, 4 H,
CH2), 3.49 (q, Et2O), 2.31 (s, 6 H, ArMe), 2.16 (s, 12 H, ArMe),
1910
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