Tashkandi et al.
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7.8 Hz), 7.44–7.32 (m, 6H, Ph-H and F), 7.32–7.28 (m, 1H, D), 7.27–
7.22 (m, 2H, B and E), 7.03 (s, 1H, L), 6.93 (d, 1H, C, J = 7.2 Hz), 6.91
(s, 2H, m-Mes H), 6.55 (s, 2H, m-Mes-H), 4.65 (s, 1H, Q), 2.32 (br s, 9H,
o,p-Mes), 2.11 (s, 3H, p-Mes), 1.64 (br s, 6H, o-Mes). 13C NMR (CDCl3,
100 Hz) ␦: 150.92 (N), 145.80 (J), 143.81 (i-Ph), 143.24 (o-Mes), 142.98
(K), 141.56 (I), 141.53 (o-Mes), 140.37 (H), 138.51 (p-Mes), 138.07 (p-
Mes), 137.71 (i-Mes), 134.81 (i-Mes), 134.06 (M), 132.91 (L), 129.40 (m-
Mes), 128.67 (o-Ph), 128.26 (m-Mes), 128.10 (m-Ph), 127.33 (p-Ph),
126.60 (C), 126.37 (E), 126.12 (B), 125.76 (F), 124.35 (D), 120.16 (G),
119.27 (A), 41.88 (GeCH), 25.56 (br s, o-Mes), 22.71 (o-Mes), 21.03
(p-Mes), 20.80 (p-Mes). High-resolution EI-MS for C39H3670Ge (m/z),
calcd.: 574.206; found: 574.204.
1 Hz), 6.92 (s, 1H, L), 6.86 (m, 1H, Ph), 6.85 (s, 4H, m-Mes2), 6.41 (s,
2H, m-Mes1), 6.39 (s, 2H, m-Mes1), 4.64 (s, 1H, Q), 4.54 (s, 1H, Q), 2.46
(s, 6H, o-Mes2), 2.43 (s, 6H, o-Mes2), 2.24–2.20 (m, T=), 2.18, 2.17 (s
each, 6H total, p-Mes2), 2.15–2.10 (m, T), 2.08–2.02 (m, R=), 1.87 (s,
3H, p-Mes1), 1.85 (s, 3H, p-Mes1), 1.80 (br s, 12H, o-Mes1), 1.80–1.77
(m, R), 1.49 (ddd, 1H, S1, J = 5.4, 6.3, 9.6 Hz), 1.26 (ddd, 1H, S=, J = 4.8,
6.3, 9.0 Hz), 1.18 (ddd, 1H, S=, J = 4.8, 6.6, 9.0 Hz), 1.07 (ddd, 1H, S1, J =
4.8, 5.4, 8.4 Hz). 13C NMR (C6D6, 150 Hz) ␦: 149.43 (N), 149.34 (N),
146.42 (J), 146.56 (J), 143.62 (o-Mes2), 143.53 (o-Mes2), 143.20 (Ph),
143.16 (K), 143.07 (Ph), 142.94 (K), 142.35 (I), 142.31 (I), 141.61 (o-Mes1),
141.58 (o-Mes1), 140.93 (2H), 138.88 (p-Mes2), 138.35 (p-Mes1), 138.29
(i-Mes1), 138.09 (i-Mes1), 135.76 (i-Mes2), 135.66 (i-Mes2), 135.12 (M),
135.05 (M), 130.11 (m-Mes2), 129.09 (m-Mes1), 129.05 (m-Mes1), 128.89
(L), 127.15 (B), 127.05 (B), 126.94 (F), 126.92 (F), 126.50 (2E), 126.37
(Ph), 126.35 (Ph), 126.31 (L), 126.30 (Ph), 126.17 (Ph), 126.14 (Ph),
126.04 (Ph), 124.75 (D), 124.71 (D), 124.65 (C), 124.63 (C), 120.79 (G),
119.90 (A and G), 119.76 (A), 42.58 (Q), 42.52 (Q), 30.41 (T), 29.79 (T=),
28.19 (R=), 25.93 (o-Mes2), 25.85 (o-Mes2), 24.53 (R), 23.21 (o-Mes1),
21.23 (p-Mes2), 20.89 (p-Mes1), 20.71 (p-Mes1), 17.96 (S=), 14.64 (S).
High-resolution EI-MS for C42H4070Ge m/z, calcd.: 614.2372; found:
614.2373. (Primes or numbers indicate the signals belong to the
same diastereomer.)
10b
Addition of ethoxyacetylene to germene 8
A solution of fluorogermane 9 (50 mg, 0.1 mmol) dissolved in
diethyl ether (3 mL) was cooled to −78 °C. t-BuLi (0.06 mL, 1.7 mol/L
in pentane, 0.1 mmol) was added slowly. The colour of the solution
changed from pale yellow to bright orange. The reaction mixture
was allowed to stir at room temperature for 2 h. An aliquot was
analyzed by 1H NMR spectroscopy (C6D6) and was found to contain
germene 8 (ϳ88%). The ether was removed in vacuo (if required),
yielding a bright orange residue. The residue was dissolved in
one of three solvents: C6D6, diethyl ether, or THF (1.1 mL).
Ethoxyacetylene (1.2 equiv.) was added directly to the germene
solution. The solvent was removed by rotary evaporation yield-
ing a yellow residue. The ratio of products (10e:14) in the crude
reaction mixture was determined by 1H NMR spectroscopy. The
product mixture was contaminated with residual alkyne and
unreacted fluorogermane 9. The mixture was separated by prepar-
ative thin layer chromatography on silica gel (hexanes and dichlo-
romethane, 50:50) to give contaminated samples of 10e and 14.
Further attempts at purification by chromatography resulted in
the hydrolysis of 10e and 14; compounds 15, 16, and 18 were
isolated from the plate. Compound 15 underwent isomerization
to 16 in solution. A third attempt to purify compounds 16 and 18
by preparative thin layer chromatography on silica gel (hexanes)
gave 16 in acceptable purity, however, 18 was contaminated with
Mes2GeOHCHR2.7
1H NMR (CDCl3, 600 MHz) ␦: 7.86 (d, 1H, D, J = 7.8 Hz), 7.74 (d, 1H,
A, J = 7.8 Hz), 7.37–7.31 (m, 4H, B, G, and C), 7.23–7.19 (m, 2H, F and
E), 6.91 (s, 2H, m-Mes-H), 6.79 (s, 1H, L), 6.51 (s, 1H, m-Mes-H), 4.45 (s,
1H, L), 2.87 (dt, 1H, P, J = 7.8, 14.4 Hz), 2.53 (dt, 1H, P, J = 7.8, 14.9 Hz),
2.32 (s, 9H, o,p-Mes), 2.08 (s, 3H, p-Mes), 1.63–1.57 (m, 8H, o-Mes and
Q), 1.4 (m, 2H, R), 0.93 (t, 3H, S, J = 7.2 Hz). 13C NMR (CDCl3, 150 Hz)
␦: 149.07 (N), 145.96 (K), 143.22 (bs, o-Mes), 142.73 (I), 141.57 (J), 141.38
(o-Mes), 140.36 (H), 138.38 (p-Mes), 138.21 (i-Mes), 137.96 (p-Mes),
135.27 (i-Mes), 133.80 (M), 129.34 (m-Mes), 129.00 (L), 128.17 (m-Mes),
126.25 (B), 126.23 (F), 125.61 (E), 124.23 (D), 123.30 (C), 120.04 (G),
118.87 (A), 42.00 (Ge-CH), 37.21 (P), 30.48 (Q), 25.5 (br s, o-Mes), 22.60
(o-Mes), 22.50 (R), 21.05 (p-Mes), 20.78 (p-Mes), 14.02(S). High-
resolution EI-MS for C37H4070Ge (m/z), calcd.: 554.2373; found:
554.2369. Anal. calcd. for C37H4070Ge: C 79.73, H 7.23; found: C
75.36, H 7.13.
10c and 10d
10e
Yellow oil contaminated with fluorene and other impurities
(1:0.8). 1H NMR (C6D6, 600 MHz) ␦: 7.96 (d, 1H, J = 7.2 Hz), 7.78 (d, 1H, J =
7.8 Hz), 7.71 (d, 1H, J = 7.8 Hz), 7.51 (d, 1H, J = 7.2 Hz), 7.35 (t, 1H, J =
7.2 Hz), ϳ7.23 (m; all for fluorenyl-H), 6.85 (s, 2H, m-Mes), 6.44 (s, 2H,
m-Mes), 5.58 (s, 1H, vinyl H), 4.58 (s, 1H, Ge-CH), 3.70 (dq, 1H, OCH, J =
16.8, 6 Hz), 3.52 (dq, 1H, OCH, J = 16.2, 6.6 Hz), 2.47 (br s, 6H, o-Mes),
2.18 (s, 3H, p-Mes), 1.90 (s, 3H, p-Mes), 1.80 (br s, 6H, o-Mes), 1.15 (t, 3H,
CH3, J = 6.6 Hz).
[Mes2Ge(fluorenyl)]2O7 (1:1:0.13) and other minor impurities. 1H
NMR (C6D6, 600 MHz) ␦: 7.79 (d, 1H, G, J = 7.8 Hz), 7.78 (d, 1H, G, J =
7.8 Hz), 7.67 (d, 1H, A, J = 7.8 Hz), 7.62 (d, 1H, A, J = 7.8 Hz), 7.57 (d,
1H, C, J = 7.8 Hz), 7.52 (d, 1H, C, J = 7.2 Hz), 7.50 (d, 2H, 2D, J = 7.2 Hz),
7.25 (m (2× td), 2H, 2E), 7.21 (t, 1H, B, J = 7.2 Hz), 7.16–7.14 (m, B + F +
Ph), 7.12 (t, F, J = 7.8 Hz), 7.07–7.02 (m, 5H, Ph), 6.99 (d, 1H, L, J =
14
Yellow oil. 1H NMR (C6D6, 600 MHz) ␦: 7.68 (d, 2H, J = 7.2 Hz), 7.29
(d, 2H, J = 7.8 Hz), 7.16 (t, 2H, J = 7.8 Hz), 7.00 (t, 2H, J = 7.2 Hz; all for
fluorenyl-H), 6.66 (s, 4H, m-Mes), 5.48 (s, 1H, vinyl H), 3.56 (q, 2H,
OCH2 J = 7.2 Hz), 2.12 (br s, 12H, o-Mes), 2.06 (s, 6H, p Mes), 0.74 (t,
3H, CH3, J = 6.6 Hz).
Published by NRC Research Press