1274
D. Koch und W. Beck • Metallkomplexe mit biologisch wichtigen Liganden, CXL
(m, br, 1H, NH), 7.01 - 7.53 (m, 8 H, C6H4F). - 13C-
NMR (CDCL): 8 = 8 .8 *, 9.1 [C5(CH3)5], 32.4*, 34.5
(CH-)), 57.0*, 58.2* (CH), 92.9* [ 7 (13C, 101Rh) = 9.2
Hz, C5(CH3)5], 93.1 [C5(CH3)5], 115.3* [d, 2/ ( 13C(6 ),
19F) = 22.9 Hz], 115.5 [d, 27(13C(6), ,9F) = 21.3 Hz],
124.0* [d, 2/ ( 13C(2), 19F)= 15.3 Hz], 124.1 [d, 2/ ( 13C(2),
19F) = 13.7 Hz], 125.4* [d, V (I3C(4), I9F) = 3.0 Hz],
128.7 [d, 3/ ( 13C(5), i9F) = 19.9 Hz], 128.85 [d, 3/ ( 13C(3),
19F) = 9.1 Hz], 128.9* [d, 37(13C(5), 19F) = 19.8 Hz],
129.1* [d, 3/ ( 13C(3), 19F) = 9.2 Hz], 132.5 [d, V (13C(4),
19F) = 4.5 Hz], 161.2* [d, ‘/ ( 13C, l9F) = 241.1 Hz, 178.1,
179.0* (COO). - IR (KBr): 3286 (m), 3227 (m), 3135
(m), 3097 (m, sh), 3060 (m, sh, NH), 2988 (m), 2966 (m),
2918 (m), 2874 (m, sh), 1625 (vs, koord. COO), 1588 (m,
sh), 1492 (s), 1455 (m), 1380 (m), 1350 (m), 1340 (m),
1312 (m, sh), 1287 (m), 1263 (m), 1229 (m), 1182 (m),
1159 (m), 1139 (m), 1098 (m), 1083 (m), 1028 (m), 946
(w), 932 (w), 908 (w), 879 (w), 861 (w), 849 (w), 803
(m), 763 (m), 647 (w), 622 (w). - IR (PE): 277 (w), 266
(m) (Rh-Cl). - C19H,4ClFN02Rh (455.76): ber. C 50.07,
H 5.31, N 3.07; gef. C 49.30, H 5.41, N 2.96.
1158 (m), 1100 (m), 1081 (m), 1035 (m), 1013 (w), 940
(w), 907 (w), 884 (m), 874 (m), 863 (m), 851 (m), 807
(m), 761 (s), 649 (w), 619 (w). - IR (PE): 279 (m, br,
Ir-Cl). - C 19H24ClFN 02Ir (545.08): ber. C 41.87, H 4.44,
N 2.57; gef. C 41.68, H 4.60, N 2.57.
Cp*RhCl(ri2-N, 0-N H 2CH(C6H4F)COO) (3)
Nach Entfernen des NaCl durch Zentrifugieren wird
das Lösungsmittel bis zur Trockene entfernt. Der gelbe
Rückstand wird zweimal in Diethylether gerührt und an-
schließend zweimal mit n -Pentan gewaschen. - Ausbeu-
te (gelbes Pulver) 0.086 g (84%). - ’H-NMR (CDC13):
8 = 1.73*, 1.75 [s, 15H, C5(CH3)5], 3.36 [„t“ , br, 37('H,
‘H] = 10.74 Hz, 1H, NH], 3.48* (br, 1H, NH), 4.03*
(br, 1H, NH), 4.48* [„t“, 37(‘H, ‘H) = 8.30 Hz, CH],
4.74 [dd, ^ ('H , 'H) = 10.74 Hz, 3/ ( ‘H, ’H) = 7.32 Hz,
1H, CH], 4.98 (br, 1H, NH), 6.97-7.38 (m, 8 H, C6H4F).
-
13C-NMR (CDCI3): 8 = 9.0*, 9.2 [C5(CH3)5], 56.7,
56.8* (CH), 93.1* [d, '/ ( l3C, 101Rh) = 9.1 Hz], 93.2 [d,
7 ( 13C, 10lRh) = 9.2 Hz] [C5(CH3)5], 115.9* [d, 2/ ( 13C(6 ),
l9F) = 21.4 Hz], 121.7* [d, V (13C, ,9F) = 13.7 Hz],
122.1 [d, V (13C, 19F) =18.3 Hz], 125.0 [d, X/ ( 13C, ,9F) =
15.3 Hz], 127.6* [d, V (13C, 19F) = 13.8 Hz], 128.0 [d,
V (13C, l9F )= 13.8 Hz], 129.7* [d, V (13C, 19F) = 6.1 Hz],
130.0 [d, X/ ( 13C, 19F) = 4.6 Hz], 130.2 [d, V (13C, 19F) =
6.1 Hz], 130.4* [d, X/ ( 13C, 19F) = 9.1 Hz], 164.3* [d,
'y(13C(l), 19F) = 282.3 Hz], 176.9* (COO). - IR (KBr):
3298 (m), 3225 (m), 3133 (m), 3090 (m, sh), 3074 (m,
sh, NH), 2981 (w, sh), 2961 (w), 2919 (m), 2872 (w),
2856 (w), 1634 (vs, koord. COO), 1587 (s), 1619 (s, sh),
1587 (m), 1493 (m), 1456 (m), 1376 (m), 1347 (m), 1311
(m), 1292 (m), 1264 (w), 1232 (m), 1221 (m), 1191 (w),
1177 (w), 1154 (m), 1102 (w), 1093 (w), 1083 (w), 1025
(m), 940 (w), 928 (w), 872 (w), 844 (w), 825 (w), 802
(w), 762 (m), 647 (w). - IR (PE): 281 (m, Rh-Cl), 266
(m, R h -C l).-C 18H22ClFN 02Rh*0.1 CH2C12 (441.74 für
C 18H22ClFN02Rh): ber. C 48.29, H 4.93, N 3.11; gef. C
48.06, H 4.92, N 2.75.
(p-Cymol)RuCl(r]2-N,0-NH2CH(C6H4F)COO) (5)
Die Synthese erfolgt nach der allgemeinen Synthe-
sevorschrift, jedoch wird die Dichlormethan-Lösung in
35 ml n-Pentan eingetropft. Den Niederschlag wäscht
man jeweils zweimal mit Diethylether und Pentan und
trocknet im Ölpumpenvakuum. Ausbeute (gelbes Pul-
ver) 0.117 g (79%). - ‘H-NMR (CDC13): 8 = 1.17* [d,
3/ ( ‘H, ‘H) = 6.84 Hz, 3H, CH(Ctf3)2], 1.18* [d, 3J('H.
*H) = 6.84 Hz, 3H, CH(C//3)2], 1.24 [d, 3/ ( ]H, ‘H) =
6.59 Hz, 3H, CH(C//3)2], 1.25 [d, 3/('H , ‘H) = 6.59 Hz,
3H, CH(CH3)2], 2.03*, 2.13 (s, 3H, ArCH3), 2.70* [sept,
3/ ( ‘H, 'H) = 6.84 Hz, 1H, C//(CH3)2], 2.13 [sept, 3J(‘H,
‘H) = 6.59 Hz, 1H, C//(CH3)2], 4.08 (br, 1H, NH), 4.23
(br, 1H, CH), 4.56* (br, 1H, CH), 5.38 - 5.60 (m, 8 H.
C6H4), 6.87 - 7.33 (m, 8 H, C6H4F), 7.80* (br, 1H, NH),
(nicht alle NH sichtbar). - 13C-NMR (CDC13): 8 = 18.87*,
18.93 (ArCH,), 22.7*, 22.9, 23.3, 23.5* [CH(CH3)2].
31.55, 31.59* [CH(CH3)2], 56.9*, 57.0 (CH), 80.1*,
80.5, 80.7, 81.2*, 82.0*, 82.3, 82.9, 83.1* (aromat. CH).
95.9*, 96.5 (aromat. C-CH3), 102.0*, 102.4 [aromat. C-
CH(CH3)2], 115.0 [d, X/ ( 13C, 19F) = 15.2 Hz], 115.5*
[d, 2J (13C(6 ), 19F) = 21.4 Hz], 115.8* [d, V (I3C, ,9F) =
12.2 Hz], 116.0 [d, V (13C, 19F) = 15.3 Hz], 125.2 [d.
V (13C, 19F) = 6.2 Hz], 126.6 [d, V (13C, 19F) = 6.1 Hz].
127.5* [d, :7(i3C(2), 19F) = 15.3 Hz], 127.7 [d, 27(13C(2),
19F) = 13.8 Hz], 129.8* [d, V (13C, l9F) = 6.1 Hz], 131.0
[d, X/ ( 13C, 19F) = 10.6 Hz], 160.2* [d], 177.3, 178.9*
(COO). - IR (KBr): 3288 (w), 3222 (w), 3120 (w, sh),
3067 (w, NH), 2965 (m) 2929 (w), 2872 (w), 2803 (w),
1638 (vs, koord. COO), 1617 (m, sh), 1587 (m), 1561 (w),
1493 (m), 1471 (w), 1457 (m), 1383 (m, sh), 1371 (m),
Cp *RhCl(r]2-N, 0-N H 2CH(CH2C6H4F )C 00) (4)
Die Synthese wird nach der allgemeinen Synthesevor-
schrift durchgeführt, jedoch wird die durch Zentrifugieren
erhaltene Dichlormethan-Lösung vorsichtig mit n-Pentan
versetzt. Es fällt ein orangefarbener Niederschlag aus,
der zweimal mit Ether und Pentan gewaschen wird. -
'H-NMR (CDCI3): 6 = 1.64*, 1.70 [s, 15H, C5(CH3)5],
2.97 [dd, 2/('H , ‘H) = 14.77 Hz, 3/('H , 'H) = 9.77 Hz,
1H, CH2], 3.03 (br, 1H, NH), 3.15* [dd, 27('H, 'H) =
14.65 Hz, 3/('H , 'H) = 8.30 Hz, 1H, CH2], 3.30* [dd,
\7('H , ’H) = 14.65 Hz, 3/('H , ]H) = 3.42 Hz, 1H, CH,],
3.52 [dd, 2/('H , 'H) = 14.77 Hz, 3J('H , ’H) = 3.67 Hz,
1H, CH2], 3.55 - 3.74 (m, 4H, CH, CH*, NH2*), 4.01
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