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Y.Z. Voloshin et al. / Inorganica Chimica Acta 358 (2005) 131–146
55.54; H, 3.41; N, 10.46; Fe, 6.98%. MS (PD): m/z 800
precipitate was washed with methanol–water (1:1) mix-
ture and dried in vacuo. Then, the solid was dissolved
in methylene dichloride and the solution was passed
through Silasorb SPH-300 layer (30 mm). The methyl-
ene dichloride elute was discarded and the desired com-
plex was eluted with acetonitrile–methylene dichloride
(1:9) mixture. This elute was evaporated to dryness
and the solid residue was reprecipitated from methyl-
ene dichloride solution with hexane. The precipitate
was washed with hexane and dried in vacuo. Yield:
0.11 g (46%). Anal. Calc. for C36H36N8O6B2F2Fe: C,
54.59; H, 4.55; N, 14.15; Fe, 7.05. Found: C, 54.46;
H, 4.52; N, 14.00; Fe, 7.00% MS (PD): m/z 791
[M]+Å. 1H NMR (CD3CN): d (ppm) 1.30 (m, 2H,
CH2), 1.46 (m, 2H, CH2), 1.69 (m, 2H, CH2), 2.50 (s,
3H, CH3), 2.91 (m, 2H, H2NCH2), 3.62 (m, 2H,
HNCH2), 6.12 (t, 1H, NH), 6.46 (br s, 2H, NH2),
7.36 (m, 20H, Ph). 13C{1H} NMR (CD3CN): d (ppm)
13.5 (s, CH3), 22.7 (s, CH2), 26.2 (s, CH2), 30.4 (s,
CH2), 40.0 (s, H2NCH2), 44.2 (s, HNCH2), 117.4 (s,
Ph), 128.0 (s, Ph), 129.8 (s, Ph), 130.3 (s, Ph), 151.5
(s, SC@N), 152.9 (s, CH3C@N), 155.7 (s, PhC@N),
156.6 (s, PhC@N). IR (cmꢀ1, KBr): 1590sh m(C@N),
934m, 994, 1065 m(N–O), 1204m m(B–O) + m(B–F).
UV–Vis (CH2Cl2): kmax (e · 10ꢀ3, molꢀ1 l cmꢀ1):
244 (27), 293 (9.3), 323 (3.8), 391 (3.5), 440 (4.8), 502
(15) nm.
Å
½Mꢂþ . H NMR (CD2Cl2): d (ppm) 2.28 (s, 3H, CH3),
1
7.28 (m, 25H, Ph). 13C{1H} NMR (CD2Cl2): 14.9 (s,
CH3), 128.3 (m, Ph), 128.9 (s, Ph), 129.3 (s, Ph),
129.4 (s, Ph), 129.9 (s, Ph), 130.4 (s, Ph), 130.7 (s,
Ph), 130.8 (two signals, Ph), 131.6 (s, Ph), 147.5 (s,
SC@N), 156.7 (s, PhC@N), 157.0 (s, PhC@N), 157.2
(s, CH3C@N). IR (cmꢀ1, KBr): 1580m m(C@N), 932,
993, 1039, 1072 m(N–O), 1220m m(B–O) + m(B–F).
UV–Vis (CH2Cl2): kmax (e · 10ꢀ3, molꢀ1 l cmꢀ1): 239
(29), 264 (6.3), 284 (13), 305 (5.6), 324 (2.9), 434
(3.8), 476 (20) nm.
3.10. FeBd2(CH3(OctS)Gm)(BF)2 (10)
Complex 7 (0.22 g, 0.3 mmol) and 10% excess of
n-octanethiol (0.057 ml, 0.33 mmol) were dissolved/sus-
pended in dry DMF (5 ml) and the solution of triethyl-
amine (0.046 ml, 0.33 mmol) in DMF (5 ml) was added
dropwise to the stirred reaction mixture. The reaction
mixture was stirred for 8 h and precipitated with water
(5 ml).The solid was reprecipitated from DMF solution
with NaClO4 saturated aqueous solution, washed with
methanol and dried in vacuo The product was dissolved
in methylene dichloride and the solution was filtered
through Silasorb SPH-300 layer (30 mm). The filtrate
was evaporated to dryness and the orange solid residue
was washed with a small amount of hexane, and then
dried in vacuo. Yield: 0.15 g (60%). Anal. Calc. for
C39H40N6O6B2F2FeS: C, 56.01; H, 4.79; N. 10.05; Fe,
3.12. FeBd2(CH3(OHCH2CH2NH)Gm)(BF)2 (12)
1
6.68. Found: C, 56.08; H, 4.68; N, 9.98; Fe, 6.69%. H
Complex 7 (0.22 g, 0.3 mmol) was dissolved/suspended
in dry 1,4-dioxane (10 ml) and the solution of an excess
of 2-ethanolamine (0.072 ml) in 1,4-dioxane (5 ml) was
added dropwise to the stirred reaction mixture for 2 h.
The reaction mixture was stirred at r.t. for 2 h and at
60 ꢁC for 1 h. The resulting dark-red solution was pre-
cipitated with water. The precipitate was washed with
methanol–water (3:1) mixture and dried in vacuo. The
solid was dissolved in chloroform and the solution was
passed through Silasorb SPH-300 layer (30 mm). The
chloroform elute was discarded and the desired complex
was eluted with acetonitrile–chloroform (1:3) mixture.
This elute was evaporated to dryness and washed with
hexane, and then dried in vacuo. Yield: 0.086 g (38%).
Anal. Calc. for C33H29N7O7B2F2Fe: C, 52.77; H, 3.86;
NMR (CDCl3): d (ppm) 0.86 (m, 3H, CH3 (Oct)), 1.26
(m, 10H, (CH2)5), 1.61 (m, 2H, CH2), 2.59 (s, 3H,
CH3 (oxime)), 3.37 (t, 2H, SCH2), 7.28–7.34 (m, 20H,
Ph), 13C{1H} NMR (CDCl3): 14.1 (s, CH3 (Oct)), 14.9
(s, CH3 (oxime)), 22.6 (s, CH2), 28.4 (s, CH2), 29.1
(two signals, CH2), 30.0 (s, CH2), 31.7 (s, CH2), 34.2
(s, SCH2), 127.9 (s, Ph), 129.1 (s, Ph), 129.2 (s, Ph),
130.0 (s, Ph), 130.8 (s, Ph), 147.8 (s, SC@N), 156.1 (m,
CH3 C@N + PhC@N). IR (cmꢀ1, KBr): 1550–1580m
m(C@N), 926m, 988, 1037, 1069 m(N–O), 1216m m(B–
O) + m(B–F). UV–Vis (CH2Cl2): kmax (e · 10ꢀ3
,
molꢀ1 l cmꢀ1): 238 (30), 265 (12), 284 (12), 300 (11),
424 (3.8), 477 (25) nm.
N, 13.06; Fe, 7.44. Found: C, 52.86; H, 3.94; N, 12.96;
Å
Fe, 7.31%. MS (PD): m/z 750 ½Mꢂþ . 1H NMR (CDCl3):
d (ppm) 2.41 (s, 3H, CH3), 2.50 (br s, 1H, OH), 3.65 (m,
4H, CH2CH2), 5.69 (br s, 1H, NH), 7.26 (m, 12H, Ph),
7.33 (m, 8H, Ph). 13C{1H} NMR (CDCl3): d (ppm)
14.3 (s, CH3), 47.0 (s, NCH2), 62.3 (s, OCH2), 127.8
(s, Ph), 129.3 (s, Ph), 129.7 (s, Ph), 130.7 (s, Ph), 151.6
(s, NC@N), 152.0 (s, CH3 C@N), 156.0 (s, PhC@N),
156.6 (s, PhC@N). IR (cmꢀ1, KBr): 1578m m(C@N),
918–930m, 985m, 1056 m(N–O), 1202m m(B–O) + m(B–
3.11. FeBd2(CH3(NH2(CH2)5NH)Gm)(BF)2 (11)
Complex 7 (0.22 g, 0.3 mmol) and an excess of cada-
verine (0.35 ml) were dissolved/suspended in dry 1,4-
dioxane (15 ml). The reaction mixture was stirred for
8 h and left overnight. Then, the dark-red product
was precipitated with water and reprecipitated from
DMF solution with NaClO4 saturated aqueous solu-
tion and from acetonitrile solution with water. The