NJC
Paper
ꢁ1
(
97.21 MHz, THF-d
8
): d = 1.17. IR (nujol, cm ): 1664 (m), 1574 (m), and the Australian Research Council Discovery Projects are
1
8
547 (w), 1226 (m), 1169 (m), 1154 (m), 1079 (w), 10718 (w), 892 (w), gratefully acknowledged. We thank Karl W. T o¨ rnroos for
44 (m), 723 (m). The elemental analysis of 6d consistently valuable help with some of the X-ray structure analyses,
revealed a carbon composition higher than expected for Manfred Steimann for providing additional starting material
iPr
Li(bimca )ꢀLiI. This outcome is likely due to the inclusion of and Jurij Kessler for a sample of 5f. We also thank the referee
THF in the solid product. EA: calcd for C32
C 59.00, H 6.19, N 10.75; found: C 59.70, H 5.53, N 11.46. NH chemical shift.
Procedure B: Solid methyllithium (3 eq.) was added to a stirred,
H
40
N
5
Liꢀ(LiI)(THF): that pointed out a possible concentration dependency of the
8
yellow suspension of the imidazolium salt 5 in THF-d (0.5 mL)
to immediately give a pale amber, blue fluorescent solution,
which was kept at room temperature for 1 h. A nearly quanti-
tative conversion of the imidazolium precursors 5 and formation
of the lithium complexes 6 was monitored by NMR spectroscopy.
Due to their high sensitivity towards air and moisture no elemental
analysis of compounds 6 were measured.
Notes and references
1 (a) C. J. Moulton and B. L. Shaw, J. Chem. Soc., Dalton Trans.,
1976, 1020–1024. Reviews: (b) P. A Chase, R. A. Gossage and
G. van Koten, Top. Organomet. Chem., 2016, 54, 1–15; on
Li-pincer: (c) R. A. Gossage, Top. Organomet. Chem., 2016, 54,
17–44.
nPr
1
8
Li(bimca ) (6c). H NMR (400.11 MHz, THF-d ): d 1.53
(
s, 18H, H-10), 1.60–1.70 (br m, 10 H, H13/14), 4.74 (m, 4H,
2 (a) E. Peris, J. A. Loch, J. Mata and R. H. Crabtree, Chem.
Commun., 2001, 201–202. Reviews: (b) R. E. Douthwaite,
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698–699.
0
H-12) 7.51 (br s, 2H, H-4 ), 7.65 (br s, 2H, H
2
THF-d ): d 24.2 (C14), 32.8 (C10), 35.1 (C11), 53.3 (C12), 111.2
(
-
2/7), 7.98 (br s,
H, H-5 ), 8.08 (br s, 2H, H-4/5). C{ H} NMR (100.61 MHz,
0
13
1
8
0
0
C2/7), 113.9 (C4/5), 116.1 (C4 ), 119.4 (C5 ), 127.9 (C4a/5a),
3 (a) M. Poyatos, J. A. Mata and E. Peris, Chem. Rev., 2009, 109,
3677–3707; (b) J. A. Mata, M. Poyatos and E. Peris, Coord.
Chem. Rev., 2007, 251, 841–859; (c) D. Pugh and A. A.
Danopoulos, Coord. Chem. Rev., 2007, 251, 610–641;
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and Functional Design, ed. L. H. Gade and P. Hofmann,
Wiley-VCH, Weinheim, 2014, pp. 183–204; (e) K. Farrell and
M. Albrecht, Top. Organomet. Chem., 2016, 54, 45–92.
4 M. Moser, B. Wucher, F. Rominger and D. Kunz, Organo-
metallics, 2007, 26, 1024–1030.
5 (a) B. Wucher, M. Moser, S. A. Schumacher, F. Rominger
and D. Kunz, Angew. Chem., Int. Ed., 2009, 48, 4417–4421;
(b) A. Seyboldt, B. Wucher, M. Alles, F. Rominger,
C. Maichle-M o¨ ssmer and D. Kunz, J. Organomet. Chem.,
2015, 775, 202–208; (c) E. J u¨ rgens, B. Wucher, F. Rominger,
K. W. T o¨ rnroos and D. Kunz, Chem. Commun., 2015, 51,
1897–1900. Group 10: (d) Ni,Pd,Pt: A. Seyboldt, B. Wucher,
S. Hohnstein, K. Eichele, F. Rominger, K. W. T o¨ rnroos and
D. Kunz, Organometallics, 2015, 34, 2717–2725. Group 11:
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Z. Naturforsch., 2016, DOI: 10.1515/znb-2016-0158.
0
1
28.3 (C1/8), 135.2 (C3/6), 143.5 (C1a/8a), 203.6 (C2 ). The C13
signal is covered by the THF signal.
Allyl
1
8
Li(bimca ) (6e). H NMR (400.11 MHz, THF-d ): d 1.49
(s, 18H, H-10), 4.89 (br s, 2H, H-12), 5.20–5.35 (m, 4H, H-14),
0
6
7
(
5
(
(
.20 (m, 2H, H-13), 7.15 (br s, 2H, H-4 ), 7.41 (br s, 2H, H-2/7),
0
13
1
.79 (br s, 2H, H-5 ), 8.00 (br s, 2H, H-4/5). C{ H} NMR
100.61 MHz, THF-d ): d 32.5 (C13), 32.7 (C10), 35.0 (C11),
8
4.5 (C12), 111.3 (s, C2/7), 114.0 (C4/5), 117.3 (C14), 118.9
0
0
C4 ), 119.6 (C5 ), 128.1 (C4a/5a and C1/8), 135.4 (C3/6), 136.4
0
C13), 143.9 (C1a/8a), 205.7 (C2 ).
Li(bimca ) (6h). H NMR (400.11 MHz, THF-d
Ph
1
8
): d 1.49
0
(s, 18H, H-10), 7.25 (br s, 2H, H-4 ), 7.20–7.30 (m, 6H, HPh),
7
.39 (br s, 2H, H-2/7), 7.67–7.70 (m, 4H, HPh), 7.76 (s br, 2H,
0
13
1
H-5 ), 7.98 (br s, 2H, H-4/5). C{ H} NMR (100.61 MHz, THF-d ):
d 32.8 (C10), 35.1 (C11), 111.8 (C2/7), 114.5 (C4/5), 118.7 (C4 ),
1
8
0
0
20.9 (C5 ), 122.3 (C ), 126.8 (C ), 127.8 (C4a/5a), 128.1 (C1/8),
Ph
Ph
0
1
30.2 (CPh), 135.6 (C3/6), 143.2 (C1a/8a), 143.5 (CPh), 205.1 (C2 ).
Li{ H} NMR (97.21 MHz, THF-d
Li(bimca ) (6i). H NMR (400 MHz, THF-d
7
1
8
): d = 0.59.
Py
1
8
): d 1.53 (s, 18H,
3
0
H-10), 7.27–7.31 (m, 2H, HPy), 7.54 (d, JHH = 1.7 Hz, 2H, H-4 ),
7
(
7
4
.60–7.70 (m, 2H, HPy), 8.00 (d, JHH = 1.7 Hz, 2H, H-2/7), 8.10
6 (a) D. C. Marelius, E. H. Darrow, C. E. Moore, J. A. Golen,
A. L. Rheingold and D. B. Grotjahn, Chem. – Eur. J., 2015, 12,
10988–10992. A mesoionic variation of the bimca ligand was
introduced by: (b) D. I. Bezuidenhout, G. Kleinhans,
G. Guisado-Barrios, D. C. Liles, G. Ung and G. Bertrand,
Chem. Commun., 2014, 50, 2431–2433.
3
0
4
d, J = 1.7 Hz, 2H, H-5 ), 8.19 (d, J
= 1.7 Hz, 2H, H-4/5),
HH
HH
1
3
1
.20–8.23 (m, 2H, H ), 8.48–8.50 (m, 2H, H ). C{ H} NMR
Py Py
(
(
(
100 MHz, THF-d ): d 32.7 (C10), 35.0 (C11), 112.4 (C2/7), 114.6
8
0
0
C4/5 or CPy), 114.8 (C4/5 or CPy), 117.3 (C4 ), 121.0 (C5 ), 122.1
C
Py), 127.7 (C4a/5a), 128.2 (C1/8), 135.5 (C3/6), 139.5 (CPy),
0
1
43.5 (C1a/8a), 149.3 (CPy), 154.4 (CPy), 205.5 (C2 ).
7 G. J. P. Britovsek, V. C. Gibson, O. D. Hoarau, S. K.
Spitzmesser, A. J. P. White and D. J. Williams, Inorg. Chem.,
2003, 42, 3454–3465.
8
(a) Y. Liu, M. Nishiura, Y. Wang and Z. Hou, J. Am. Chem.
Soc., 2006, 128, 5592–5593; (b) A. Rembiak and A. M. P.
Koskinen, Synthesis, 2015, 3347–3353.
Acknowledgements
Financial support from the BMBF and MWK-BW (Professorin-
nenprogramm, LGF scholarship for E. J.), German academic
exchange service (DAAD, scholarship for K. B.), Australian
government (Australian Postgraduate Award scholarship for K. B.),
9 (a) M. Inoue, T. Suzuki and M. Nakada, J. Am. Chem. Soc.,
2003, 125, 1140–1141; (b) A. Hamerurlaine and W. Dehaen,
Tetrahedron Lett., 2003, 44, 957–959; (c) A. Treibs and
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