Article
Organometallics, Vol. 29, No. 16, 2010 3659
Table 1. Summary of Crystallographic Data for Compounds 3-7
3
4
5
6
7
empirical formula
fw
cryst syst
C
609.83
monoclinic
P21/n
12.625(3)
18.369(4)
15.562(3)
90
110.27(3)
90
3385.5(12)
4
1.196
1.008
1304
35H53ClGeN2
C35H53ClN2Sn
655.93
monoclinic
P21/n
12.5810(6)
18.6731(7)
15.7415(6)
90
111.903(5)
90
3431.2(2)
4
1.270
0.847
1376
C27H44GeLiNO
478.16
triclinic
P1
9.3348(3)
10.7638(3)
14.9412(5)
92.791(2)
107.011(3)
108.743(3)
1342.46(7)
2
C27H44LiNOSn
524.26
triclinic
P1
9.4259(2)
9.9475(3)
15.6200(4)
78.139(2)
78.782(2)
75.844(2)
1373.64(6)
2
C47H71GeN3
750.66
orthorhombic
Pbca
14.437(3)
20.288(4)
29.679(6)
90
90
90
8693(3)
8
1.147
0.738
3248
space group
˚
a (A)
˚
b (A)
˚
c (A)
R (deg)
β (deg)
γ (deg)
3
˚
vol (A )
Z
F(calcd) (g cm-3
)
1.183
1.158
512
1.268
0.947
548
μ (mm-1
F(000)
)
cryst size (mm)
θ range (deg)
reflns collected
Rint
unique reflns
goodness of fit
temp (K)
0.25 ꢀ 0.20 ꢀ 0.15
2.94 to 25.34
11 442
0.0449
6079
0.25 ꢀ 0.20 ꢀ 0.12
2.90 to 25.24
32 845
0.1005
6190
0.20 ꢀ 0.15 ꢀ 0.10
3.11 to 26.99
12 920
0.0276
5827
0.20 ꢀ 0.20 ꢀ 0.10
3.15 to 27.00
14 847
0.0171
5974
0.50 ꢀ 0.45 ꢀ 0.30
3.00 to 28.00
20 008
0.0215
10 470
1.014
150(2)
1.050
173(2)
0.990
173(2)
1.068
173(2)
1.023
123(2)
R1 indices [I > 2σ(I)]
wR2 indices (all data)
0.0386
0.0858
0.0580
0.0778
0.0368
0.0818
0.0271
0.0661
0.0306
0.0774
Experimental Section
123.9, 125.1, 127.3, 141.6, 144.5, 146.3 (Ar-C), 173.2 (CBut); IR
ν/cm-1 (Nujol) 1548w, 1378s, 1359m, 1312m, 1260m, 1130m,
1098m, 798m, 785m; MS (EI 70 eV), m/z (%) 610.3 (Mþ, 25),
575.3 (Mþ - Cl, 15), 244.1 (DipNCCButHþ, 100). Anal. Calcd
for C35H53ClGeN2: C 68.93, H 8.76, N 4.59. Found: C 68.94, H
8.63, N 4.61.
General Methods. All manipulations were carried out using
standard Schlenk and glovebox techniques under an atmo-
sphere of high-purity dinitrogen or argon. THF and hexane
were distilled over potassium, while diethyl ether was distilled
over Na/K alloy. 1H and 13C{1H} NMR spectra were recorded
on either Bruker DXP300 or DPX400 spectrometers and were
Preparation of [(THF)Li{η5-GeC(But)C(H)C(But)N(Dip)}]
(5) and [(ButNacnac)Ge{N(H)(Dip)}] (7). To a slurry of lithium
powder (40 mg, 5.7 mmol) in THF (40 mL) at -80 °C was added
a solution of 3 (0.15 g, 0.25 mmol) in THF (40 mL) over 5 min.
The mixture was warmed to 20 °C and stirred overnight. All
volatiles were subsequently removed in vacuo, and the residue
was extracted into hexane (15 mL). The extract was filtered and
stored at -30 °C overnight to yield yellow crystals of 5 (0.05 g,
83%). The mother liquor was concentrated to ca. 7 mL and
stored at -30 °C overnight to yield orange crystals of 7 (0.035 g,
37%). Data for 5: mp 137-139 °C; 1H NMR (300 MHz, C6D6,
298 K) δ 1.20 (d, 3JHH = 6.9 Hz, 6 H, CH(CH3)2), 1.23 (br m, 4
H, THF-CH2), 1.26 (s, 9 H, NCC(CH3)3), 1.48 (d, 3JHH = 6.9
Hz, 6 H, CH(CH3)2), 1.65 (s, 9 H, GeCC(CH3)3), 2.64 (sept,
3JHH = 6.9 Hz, 2 H, CH(CH3)2), 3.37 (br m, 4 H, THF-OCH2),
7.08 (s, 1 H, NCCH), 7.12-7.34 (m, 3 H, Ar-H); 13C{1H} NMR
(75 MHz, C6D6, 300 K) δ 22.6 (CH(CH3)2), 23.0 (CH(CH3)2),
25.3 (THF-CH2), 28.5 (CH(CH3)2), 33.2 (NCC(CH3)3), 35.1
(GeCC(CH3)3), 37.4 (NCC(CH3)3), 37.8 (GeCC(CH3)3), 68.7
(THF-OCH2), 112.5 (NCCH), 123.1, 125.8, 132.0, 146.4 (Ar-C),
147.5 (NCC), 194.7 (GeCC); 7Li{1H} NMR (155.4 MHz, C6D6,
300 K) δ -5.31; IR ν/cm-1 (Nujol) 1664w, 1546w, 1466 m,
1245s, 1190m, 1135m, 985m, 801m, 758m, 719w; MS (EI 70 eV),
m/z (%) 328.3 (DipNC(But)C(H)C(But)Hþ, 10), 270.2
(DipNC(But)C(H)CHþ, 100). Anal. Calcd for C27H44GeLiNO:
C 67.82, H 9.27, N 2.93. Found: C 67.61, H 9.01, N 2.86. Data
for 7: mp 155-160 °C (dec); 1H NMR (300 MHz, C6D6, 298 K) δ
referenced to the resonances of the solvent used. Li{1H} and
7
119Sn{1H} NMR spectra were recorded on a Bruker Avance 400
spectrometer and were referenced to external 1 M aqueous LiCl
and SnMe4, respectively. Mass spectra were obtained from the
EPSRC National Mass Spectrometric Service at Swansea Uni-
versity. IR spectra were recorded using a Nicolet 510 FT-IR
spectrometer as Nujol mulls between NaCl plates. Micro-
analyses were carried out by Campbell Microanalytical, Ottago.
A reproducible microanalyses could not be obtained for 6 due to
its thermal instability at ambient temperature in the solid state.
Melting points were determined in sealed glass capillaries under
dinitrogen and are uncorrected. The compounds ButNacnacH29
and [(ButNacnac)SnCl]17 were prepared by variations of litera-
ture procedures. All other reagents were used as received.
Preparation of [(ButNacnac)GeCl] (3). A solution of 1.6 M
BunLi in hexane (0.63 mL, 1.0 mmol) was added to a solution
of ButNacnacH (0.50 g, 1.0 mmol) in diethyl ether (15 mL) at
-80 °C over 5 min. The solution was warmed to ambient tempera-
ture and stirred for 2 h, after which time it was cooled to -80 °C
and a suspension of GeCl2 dioxane (0.23 g, 1.0 mmol) in diethyl
3
ether (15 mL) at -80 °C was added to it. The reaction mixture
was warmed to room temperature and stirred for 2 h, where-
upon volatiles were removed in vacuo. The residue was extracted
into hexane (40 mL), and the extract filtered and stored at -30 °C
overnight to yield yellow crystals of 3 (0.37 g, 61%): mp 231-
233 °C; 1H NMR (300 MHz, C6D6, 298 K) δ 1.05 (d, 3JHH
=
=
3
6.9 Hz, 6 H, CH(CH3)2), 1.11 (s, 18 H, C(CH3)3), 1.17 (d, 3JHH
1.01, 1.13, 1.20, 1.22, 1.23, 1.33 (6d, JHH = 6.9 Hz, 36 H,
CH(CH3)2), 1.13 (s, 18 H, C(CH3)3), 2.83 (sept, 3JHH = 6.9 Hz,
1 H, CH(CH3)2), 3.18 (sept, 3JHH = 6.9 Hz, 2 H, CH(CH3)2), 3.24
(sept, 3JHH = 6.9 Hz, 2 H, CH(CH3)2), 3.24 (sept, 3JHH = 6.9
Hz, 1 H, CH(CH3)2), 4.85 (s, 1 H, NH), 6.15 (s, 1 H, NCCHCN),
6.86-7.13 (m, 9 H, Ar-H); 13C{1H} NMR (75 MHz, C6D6, 300
K) δ 23.1, 23.9, 25.2, 26.6, 26.8, 27.4 (6 ꢀ CH(CH3)2), 28.6, 28.7,
28.8, 29.1 (4 ꢀ CH(CH3)2), 32.3 (C(CH3)3), 42.5 (C(CH3)3),
101.3 (NCCCN), 117.8, 121.8, 124.1, 124.7, 125.6, 126.8, 135.2,
137.5, 143.4, 144.1, 145.7, 146.0 (Ar-C), 174.1 (CBut); IR ν/cm-1
3
6.9 Hz, 6 H, CH(CH3)2), 1.30 (d, JHH = 6.9 Hz, 6 H, CH-
3
(CH3)2), 1.52 (d, JHH = 6.9 Hz, 6 H, CH(CH3)2), 2.97 (sept,
3JHH = 6.9 Hz, 2 H, CH(CH3)2), 4.05 (sept, 3JHH = 6.9 Hz, 2 H,
CH(CH3)2), 6.41 (s, 1 H, NCCHCN); 13C NMR (75 MHz,
C6D6, 298 K) δ 24.3, 24.5, 26.3, 28.3 (CH(CH3)2), 28.4, 28.5
(CH(CH3)2), 31.9 (C(CH3)3), 41.9 (C(CH3)3), 105.6 (NCCCN),
(29) Budzelaar, P. H. M.; van Oort, A. B.; Orpen, A. G. Eur. J. Inorg.
Chem. 1998, 1485.