European Journal of Inorganic Chemistry
10.1002/ejic.201600884
FULL PAPER
+
+
NMR (C
OCH CH
MHz) δ
6
D
6
, 400 MHz)
), 3.84 (q, 2H, OCH
13.7 (OCH CH ), 27.4 (COC(CH
), 176.0 (COC(CH ). FT-IR (νmax/cm ): 3226s, 2979s, 1652s,
δ
H
1.10 (s, 9H, COC(CH
3
3
)
3
), 1.16 (t, 3H,
), 8.20(s, 1H, NH). C NMR (C , 100
), 37.9 (COC(CH ), 71.4
[Ge(empa)
[PrCO] (75%).
2
]: 334 [M] ; found 334 (60%), 204 [Ge(empa)] (65%), 71
1
i
+
2
3
2
CH
3
6
D
)
3 3
6
C
2
3
3
)
3
−
1
(
2
OCH CH
3
3 3
)
Ge(mdpa)
mdpaH) (0.64 g, 4.84 mmol) in hexane (10 mL) was added dropwise to
a stirring hexane solution (20 mL) of Ge(btsa) (1.0 g, 2.42 mmol). After
2
(3): A solution of N-Methoxy-2,2-dimethylpropanamide
1
1
506s, 1483s, 1462m, 1399w, 1386w, 1368w, 1294w, 1229w, 1159w,
123w, 1091w, 1057s, 1029m, 1009m, 933m, 863w, 812w, 598w. Anal.
(
2
7 2
Calcd for C H15NO : C, 57.90; H, 10.41; N, 9.65. Found: C, 57.88; H,
being left to react overnight rat room temperature, the volatiles were
removed in vacuo and the crude product was sublimed at (60 °C /10
+
1
0.38; N, 9.61. EI-MS: m/z calcd for [edpaH]: 145 [M] ; found 145 (30%),
−1
+
t
+
t
+
3
130 [M-CH ] (30%), 85 [ BuCO] (75 %), 57 [ Bu] (100%).
Torr) to afford the pure complex as a white solid. Yield: 0.40 g (49%). Mp
1
4
OCH
7 °C. H NMR (C
6
D
6
, 400 MHz) δ
NMR (C 100 MHz)
3 3
), 59.5 (OCH ), 170.3 (COC(CH )
H
1.25 (s. 9H, COC(CH
28.1 (COC(CH
). FT-IR (νmax/cm ):
3
)
3
), 3.70 (s, 3H,
13
N-Methoxybenzamide (mbaH): O-methyl hydroxylamine hydrochloride
5.26 g, 63.0 mmol) was added to a solution of K CO (24.9 g, 180 mmol)
3
).
C
6 6
D
,
δ
C
3 3
) ), 35.3
−
1
(
2
3
(COC(CH
3
)
3
3
in an ethyl acetate/water mixture (150 mL, 2:1). The above mixture was
cooled to 0 °C in an ice bath and benzoyl chloride (8.43 g, 60.0 mmol)
was added dropwise. The reaction mixture was then allowed to warm to
room temperature and stirred for another 12 hours. Upon reaction
completion, the reaction mixture was quenched with ice cold water and
the organic layer was separated. Subsequently, the aqueous layer was
extracted with ethyl acetate (20 mL 3). The combined organic layers
2976m, 2941m, 2869w, 1588s, 1480m, 1460w, 1394w, 1367w, 1328m,
1224w, 1186s, 1036s, 943w, 846w, 788w, 731w, 632w, 613w, 535w,
484w. Anal. Calcd for C12
C, 43.15; H, 7.41; N, 8.38. EI-MS: m/z calcd for [Ge(mdpa)
found 334 (47%), 204 [Ge(mdpa)] (35%), 57 [ Bu] (100%).
2 4
H24GeN O : C, 43.29; H, 7.27; N, 8.41. Found:
+
2
]: 334 [M] ;
+
t
+
Ge(edpa)
0.70 g, 4.84 mmol) in diethyl ether (10 mL) was added dropwise to a
stirring diethyl ether solution (20 mL) of Ge(btsa) (1.0 g, 2.42 mmol).
2
(4): A solution of N-Ethoxy-2,2-dimethylpropanamide (edpaH)
were dried over anhydrous MgSO
4
, filtered, and solvents were removed
(
under reduced pressure. The pure product was obtained as a colorless
2
−
1
liquid via distillation at 90 °C/ 10 Torr, and solidified as a white solid
After being left to react overnight at room temperature, the volatiles were
1
after cooling. Yield: 7.26 g (80%). H NMR (C
H, OCH ), 7.06 (m, 3H, Ph), 7.83 (d, 2H, Ph), 10.18 (s, 1H, NH).
NMR (CDCl , 100 MHz) δ 63.9 (OCH ), 127.2 (Ph-C), 128.4 (Ph-C),
31.8 (Ph-C), 166.3 (CO). FT-IR (νmax/cm ): 3202s, 2978s, 2937m,
6
D
6
, 400 MHz) δ
H
3.59 (s,
−1
removed in vacuo and the crude product was distilled (10 Torr) to afford
1
3
3
3
C
1
the pure product as a colorless liquid at 80 °C. Yield: 0.45 g (51%).
NMR (C , 400 MHz) δ 1.25 (m, br, 12H, OCH CH & COC(CH
, 100 MHz) δ 15.3 (OCH CH
), 35.5 (COCH(CH ), 69.6 (OCH CH ), 169.7
). FT-IR (νmax/cm ): 2977s, 2932w, 2870w, 1589s, 1482m,
H
3
C
3
D
3 3
)
),
6
6
H
13
2
3
−
1
1
2
1
6
6
1
4
2
(
.18 (q, 2H, OCH
8.1 (COCH(CH
COCH(CH )
3 3
2
CH
3
). C NMR (C
D
6 6
C
2
3
),
815w, 1654s, 1601w, 1579s, 1516s, 1482s, 1438m, 1308s, 1190w,
152m, 1075w, 1044s, 1025s, 943m, 880s, 798m, 713s, 692s, 674s,
H NO : C, 63.56; H, 6.00; N, 9.27. Found: C,
8 9 2
3.55; H, 5.96; N, 9.22. EI-MS: m/z calcd for [mbaH]: 151 [M] ; found
3
)
3
3
)
3
2
3
−
1
08m. Anal. Calcd for C
1
1
6
4
458w, 1395m, 1386m, 1359w, 1329s, 1292w, 1224w, 1188s, 1121m,
092w, 1041s, 960w, 938w, 905m, 854w, 811w, 792w, 778w, 729 w,
+
+
+
51 (30%), 105 [PhCO] (100%), 77 [Ph] (45%).
2 4
33m, 614m, 530w, 477w, 445w. Anal. Calcd for C14H28GeN O : C,
6.58; H, 7.82; N, 7.76. Found: C, 46.52; H, 7.78; N, 7.72. EI-MS: m/z
+
+
Germanium Complexes
calcd for [Ge(edpa)
2
]: 362 [M] ; found 362 (7%), 218 [Ge(edpa)] (7%),
+
t
+
145 [edpaH] (17%), 57 [ Bu] (100%).
Ge(mpa)
mmol) in diethyl ether (10 mL) was added dropwise to a stirring diethyl
ether solution (20 mL) of Ge(btsa) (1.0 g, 2.42 mmol). After being left to
react overnight at room temperature, the volatiles were removed in vacuo
2
(1): A solution of N-methoxypropanamide (mpaH) (0.50 g, 4.84
2
Ge(mba) (5): A solution of N-Methoxybenzamide (mbaH) (0.73 g, 4.84
2
mmol) in diethyl ether (10 mL) was added dropwise to a stirring diethyl
ether solution (20 mL) of Ge(btsa) (1.0 g, 2.42 mmol). After being left to
2
−
1
and the crude product was distilled (10 Torr) to afford the pure complex
react overnight at room temperature, the volatiles were removed in vacuo
to yield the crude product as a white solid. The pure product was
1
as a colorless liquid at 120 °C. Yield: 0.22 g (33%). H NMR (C
MHz) δ 1.02 (t, 3H, COCH CH ), 2.11 (q, 2H, COCH CH ), 3.69 (s, 3H,
100 MHz) 10.9 (COCH CH ), 23.6
), 166.0 (COCH CH ). FT-IR (νmax/cm ):
6
D
6
, 400
H
2
3
2
3
obtained via recrystallization from a hexane solution at 0 °C as colorless
13
1
OCH
(
3
).
C
NMR (C
6
D
6
,
δ
C
2
3
crystals. Yield: 0.38 g (42%). Mp 132 °C. H NMR (C
6
13
D
6
, 400 MHz) δ
H
−
1
2
COCH CH
3
), 59.5 (OCH
3
2
3
3.85 (s, 3H, OCH
3
), 7.00 (m, 3H, Ph), 8.01 (m, 2H, Ph). C NMR (CDCl
3
,
2
1
979m, 2942m, 2829w, 1615m, 1464m, 1438m, 1379m, 1355m, 1288m,
270m, 1191w, 1042s, 999m, 902m, 845m, 623w, 474w. Anal. Calcd for
100 MHz) δ 60.9 (OCH
C
3
), 127.2 (Ph), 128.3 (Ph). 130.4 (CPh), 130.5
−1
(Ph), 161.7 (CO). FT-IR (νmax/cm ): 3065w, 3003w, 2940m, 2816w,
1595m, 1558s, 1518w, 1352s, 1306w, 1185w, 1116m, 1043w, 1026s,
1015m, 908w, 830w, 780w, 703m, 691s, 680s, 584w, 564w, 506w, 440w.
8 2 4
C H16GeN O : C, 34.71; H, 5.83; N, 10.12. Found: C, 34.12; H, 5.73; N,
+
2
9.91. EI-MS: m/z calcd for [Ge(mpa) ]: 278 [M] ; found 278 (20%), 176
+
+
[
Ge(mpa)] (25%), 57 [EtCO] (100%).
2 4
Anal. Calcd for C16H16GeN O : C, 51.53; H, 4.32; N, 7.51. Found: C,
+
2
51.15; H, 4.25; N, 7.42. EI-MS: m/z calcd for [Ge(mba) ]: 374 [M] ; found
+
+
+
374 (50%), 224 [Ge(mba)] (10%),105 [PhCO] (100%), 77 [Ph] (50%).
2
Ge(empa) (2): A solution of N-ethoxy-2-methylpropanamide (empaH)
(
0.64 g, 4.84 mmol) in diethyl ether (10 mL) was added dropwise to a
stirring diethyl ether solution (20 mL) of Ge(btsa) (1.0 g, 2.42 mmol).
After being left to react overnight at room temperature, the volatiles were
2
Tin Complexes
−
1
removed in vacuo and the crude product was distilled (10 Torr) to afford
Sn(mpa)
mmol) in diethyl ether (10 mL) was added dropwise to a stirring diethyl
ether solution (20 mL) of Sn(btsa) (1.1 g, 2.4 mmol). After being left to
react overnight at room temperature, the volatiles were removed in vacuo
2
(6): A solution of N-methoxypropanamide (mpaH) (0.50 g, 4.84
1
the pure complex as a colorless liquid at 100 °C. Yield: 0.38 g (47%).
NMR (C , 400 MHz) δ 1.15 (d, 6H, COCH(CH ), 1.26 (t, 3H,
OCH CH ), 2.57 (m, 1H, COCH(CH ), 4.14 (m, 2H, OCH
NMR (C , 100 MHz) δ 15.2 (OCH CH ), 20.1 (COCH(CH
), 69.6 (OCH CH ), 168.0 (COCH(CH ). FT-IR (νmax/cm ):
H
6
D
6
H
3 2
)
2
13
2
3
3
)
2
2 3
CH ).
C
−
1
6
D
6
C
2
3
3 2
)
), 30.3
and the crude product was distilled (10 Torr) to afford the pure complex
−
1
(
COCH(CH
3
)
2
2
3
3
)
2
1
as a colorless liquid at 85 °C. Yield: 0.35 g (45%). H NMR (C
MHz) δ 1.13 (t, 3H, COCH CH ), 2.24 (q, 2H, COCH CH ), 3.66 (s, 3H,
100 MHz) 11.2 (COCH CH ), 24.7
), 167.8 (COCH CH ). FT-IR (νmax/cm ):
6 6
D , 400
2
1
6
7
973s, 2935m, 2876m, 1600s, 1471m, 1386m, 1341m, 1288m, 1262m,
165m, 1122m, 1095m, 1076m, 1043s, 966w, 906m, 883m, 848w, 816w,
H
2
3
2
3
13
OCH
(
3
).
C
NMR (C
6
D
6
,
δ
C
2
3
8 2 4
80w, 620w, 526w, 486w. Anal. Calcd for C H16GeN O : C, 43.29; H,
−1
2
COCH CH
3
), 59.6 (OCH
3
2
3
.27; N, 8.41. Found: C, 43.75; H, 7.71; N, 8.58. EI-MS: m/z calcd for
2
1
971m, 2939m, 2818w, 1585s, 1468m, 1384w, 1353m, 1288m, 1271m,
190w, 1077w, 1038s, 1001w, 930w, 826w, 798w, 672w, 603w, 496w,
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