1554
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 7, July, 2003
Voloshin et al.
pentacyclo[11. 11. 11. 0 4, 9. 01 5 , 2 0.0 2 5 , 3 0]ditriacontaꢀ
,9,14,20,24,30ꢀhexaene(2–)iron(2+), FeNx (BC≡CPh) (3).
cyclo[11.11.11.04,9.015,20.025,30]ditriacontaꢀ3,9,14,20,24,30ꢀ
3
hexaene(2–)iron(2+), FeNx (BC H C H ) (6). Nioxime
3
2
3
6
4
6
5 2
The [Fe(H Nx) ]Cl complex (0.55 g, 1 mmol) was disꢀ
(0.21 g, 1.5 mmol), Fe(BF ) •6H O (0.17 g, 0.5 mmol), and
2
3
2
4 2 2
solved/suspended in EtOH (10 mL) and then the
NH )[B(C≡CPh) ] salt (0.99 g, 2.2 mmol) was added. The
biphenylylboronic acid (0.20 g, 1 mmol) were dissolved/susꢀ
pended in MeOH (10 mL) and the reaction mixture was stirred
for 2 h. The yellowꢀbrown precipitate that formed was repreꢀ
cipitated from a chloroform solution with an excess of hexane
(1 : 3) and dried in vacuo. The yield was 0.18 g (45%). Found (%):
C, 61.43; H, 5.31; N, 10.65; Fe, 7.27. C40H42B FeN O . Calcuꢀ
(
4
4
reaction mixture was refluxed with stirring for 5 h. The orangeꢀ
yellow precipitate that formed was filtered off, washed with EtOH
and Et O, dissolved in a minimal volume of CHCl , and filtered.
2
3
The filtrate was precipitated with an excess of heptane (1 : 5 v/v)
and dried in vacuo. The yield was 0.51 g (73%). Found (%):
C, 58.11; H, 4.77; N, 11.96; Fe, 7.97. C34H34B FeN O . Calcuꢀ
2
6
6
lated (%): C, 61.59; H, 5.39; N, 10.78; Fe, 7.16. MS, m/z:
+
• 1
799 [M] . H NMR (CDCl ), δ: 1.67 (m, 12 H, βꢀCH ); 2.86
2
6
6
3
2
13
1
lated (%): C, 58.34; H, 4.86; N, 12.01; Fe, 7.98. MS, m/z:
(m, 12 H, αꢀCH ); 7.50 (m, 18 H, Ar). C{ H} NMR (CDCl ),
2 3
+• 1
6
99 [M] . H NMR (CDCl ), δ: 1.78 (m, 12 H, βꢀCH ); 2.95
δ: 21.5 (βꢀCH ); 26.2 (αꢀCH ); 126.2, 127.1, 128.7, 132.2, 140.4,
2 2
3
2
–
1
(
m, 12 H, αꢀCH ); 7.26 (m, 6 H, Ph); 7.53 (m, 4 H, Ph).
141.9 (Ar); 151.8 (C=N). IR (KBr), ν/cm : 1599 (C=N);
2
1
3
1
C{ H} NMR (CDCl ), δ: 21.2 (βꢀCH ); 26.2 (αꢀCH ); 65.6,
942, 967, 1068 (N—O); 1206 (B—O). UVꢀVis (CHCl ),
3
2
2
3
λmax/nm (ε•10–3/L mol cm ): 254 (41); 285 (21); 303 (7.2);
–1
–1
9
4.4 (C≡C); 123.7, 127.7, 132.0 (Ph); 151.8 (C=N). IR (KBr),
–1
ν/cm : 1582 (C=N); 940, 1076 (N—O); 1205 (B—O); 2202
333 (3.2); 450 (15).
–1
–1
(
(
C≡C). UVꢀVis (CHCl ), λ /nm (ε•10–3/L mol cm ): 243
45); 280 (21); 305 (3.9); 351 (2.4); 448 (17).
Complex 1,12ꢀbis(tertꢀbutyl)ꢀ2,11,13,22,23,32ꢀhexaꢀ
oxaꢀ3 , 10, 14, 21, 24, 31ꢀhexaazaꢀ1, 12ꢀdiborapentaꢀ
Complex 1,8ꢀbis(2ꢀdibenzo[b,d]thienyl)ꢀ4,5,11,12,17,18ꢀ
hexachloroꢀ2,7,9,14,15,20ꢀhexaoxaꢀ3,6,10,13,16,19ꢀhexaꢀ
azaꢀ1,12ꢀdiborabicyclo[6.6.6]eicosaꢀ3,5,10,12,16,18ꢀhexaꢀ
ene(2–)iron(2+), Fe(Cl Gm) (Bdbt) (7). Dichloroglyoxime
3
max
2
3
2
cyclo[11.11.11.04 .0
,9
15,20 25,30
.0
]ditriacontaꢀ3,9,14,20,24,30ꢀ
(0.50 g, 3.2 mmol) and 2ꢀdibenzo[b,d]thienylboronic acid
(0.50 g, 3.3 mmol) were dissolved/suspended in dry MeNO2
(15 mL) with stirring. The reaction mixture was brought to
t
hexaene(2–)iron(2+), FeNx (BBu ) (4). tertꢀButylboronic acid
3
2
(
(
0.2 g, 1.8 mmol), FeCl •4H O (0.16 g, 0.8 mmol), and nioxime
0.35 g, 2.4 mmol) were dissolved/suspended in MeOH (10 mL)
2 2
reflux and then Fe(MeCN) Cl2 (0.29 g, 1 mmol), which was
4
2
and the reaction mixture was stirred for 30 min. The redꢀbrown
precipitate that formed was filtered off, washed with MeOH,
dried in air, and dissolved in a 1 : 1 CH Cl —hexane mixture.
prepared according to a known procedure, was added. The
reaction mixture was refluxed with stirring for 10 h. Then a large
excess of water was added. The resulting oilꢀlike precipitate was
2
2
The resulting solution was filtered through a layer of SPHꢀ300
silica gel (Chemapol) and the solvent was evaporated in vacuo.
The oilꢀlike residue was precipitated with MeOH. The orangeꢀ
yellow finely crystalline product was filtered off and dried in
vacuo. The yield was 0.24 g (49%). Found (%): C, 51.04; H, 6.89;
N, 13.64; Fe, 9.15. C26H42B FeN O . Calculated (%): C, 51.03;
dissolved in CHCl and filtered. An excess of hexane (1 : 3) was
3
added to the filtrate and the precipitate that formed was dried in
vacuo. The yellowꢀbrown product was dissolved in CH Cl and
2
2
filtered through a SPHꢀ300 silica gel (Chemapol) layer. The
filtrate was concentrated in vacuo to a small volume and precipiꢀ
tated with hexane (1 : 3 v/v). The yellowꢀorange finely crystalꢀ
line precipitate was filtered off, washed with hexane, and dried
in vacuo. The yield was 0.073 g (8%). Found (%): C, 39.47;
H, 1.48; N, 9.37; Fe, 6.24. C30H14B Cl FeN O S . Calculated
2
6
6
+• 1
H, 6.87; N, 13.74; Fe, 9.13. MS, m/z: 611 [M]
.
H NMR
(
(
2
1
(
CDCl ), δ: 0.92 (s, 18 H, Me); 1.78 (m, 12 H, βꢀCH ); 2.87
3
2
13
1
m, 12 H, αꢀCH ). C{ H} NMR (CDCl ), δ: 21.6 (βꢀCH );
2 3 2
2
6
6
6 2
–
1
–1
5.8 (αꢀCH ); 27.0 (Mе); 150.9 (C=N). IR (KBr), ν/cm
:
(%): C, 39.62; H, 1.54; N, 9.24; Fe, 6.14. IR (KBr), ν/cm
:
2
577 (C=N); 938, 1037 (N—O); 1079 (B—O + N—O). UVꢀVis
1522 (C=N); 937 m; 992 (N—O); 1210—1230 m (B—O). UVꢀVis
CHCl ), λ /nm (ε•10–3/L mol cm ): 247 (8.3); 281 (5.8);
–1
–1
(CHCl ), λmax/nm (ε•10 /L mol cm ): 238 (63); 260 (27);
–3
–1
–1
3
max
3
2
96 (2.3); 395 (3.0); 450 (16).
Complex 1,12ꢀbis(pyrimidinꢀ6ꢀyl)ꢀ2,11,13,22,23,32ꢀ
hexaoxaꢀ3,10,14,21,24,31ꢀhexaazaꢀ1,12ꢀdiborapentaꢀ
288 (16); 312 (11); 363 (2.5).
Xꢀray diffraction study. Single crystals of clathrochelates 1,
3, and 7 suitable for Xꢀray diffraction analysis were grown by
slow concentration of saturated solutions of the complexes in
4
,9 15,20 25,30
cyclo[11.11.11.0 .0
.0
]ditriacontaꢀ3,9,14,20,24,30ꢀ
hexaene(2–)iron(2+), FeNx (Bpmd) (5). Complex 5 was preꢀ
the CHCl —heptane (1 : 2), toluene—isooctane (1 : 2), and
3
2
3
pared analogously to complex 4 with the difference that
pyrimidinꢀ6ꢀylboronic acid (0.25 g, 1.6 mmol) was used instead
of tertꢀbutylboronic acid. The reaction time was increased to 8 h.
The resulting yellowꢀbrown product was washed with MeOH,
CH Cl —heptane (1 : 3) mixtures, respectively.
2
2
The principal crystallographic data for these compounds are
listed in Table 1. The Xꢀray data were collected on automated
Bruker SMART 1K CCD (compounds 1 and 7) and Enrafꢀ
Nonius CAD 4 (complex 3) diffractometers, λ(MoꢀKα) =
0.71073 Å. The intensities of all reflections were corrected for
Et O, and hexane and then dried in vacuo. The yield was 0.49 g
2
(
85%). Found (%): C, 43.26; H, 4.06; N, 19.36; Fe, 7.68.
2
4,25
C26H30B FeN10O10. Calculated (%): C, 43.37; H, 4.17; N, 19.46;
the Lorentz and polarization factors.
The semiempirical abꢀ
2
1
Fe, 7.76. H NMR (DMSOꢀd ), δ: 1.71 (m, 12 H, βꢀCH ); 2.77
sorption correction was applied using the SADABS program
6
2
2
6
(
4
m, 12 H, αꢀCH ); 7.23 (m, 2 H, CH); 10.60 (br. signal,
(1 and 7) and the standard ψ scanning technique.
2
13
1
H, NH). C{ H} NMR (DMSOꢀd ), δ: 20.9 (βꢀCH ); 25.9
The structures were solved by direct methods and refined by
the fullꢀmatrix leastꢀsquares method against F 2 with anisotropic
displacement parameters for nonhydrogen atoms (isotropic disꢀ
placement parameters for the apical substituents in the structure
of 3 and disordered atoms in all three structures) using the
6
2
(
αꢀCH ); 143.4 (pmd); 151.8 (C=N); 152.0, 165.9 (pmd).
2
–
1
IR (KBr), ν/cm : 1583 (C=N); 930, 963, 1062 (N—O); 1207
–1
–1
(
2
B—O). UVꢀVis (DMSO), λmax/nm (ε•10–3/L mol cm ):
59 (26); 284 (8.6); 300 (5.1); 346 (2.7); 449 (17).
Complex 1,12ꢀbis(biphenylyl)ꢀ2,11,13,22,23,32ꢀhexaꢀ
oxaꢀ3, 10, 14, 21, 24, 31ꢀhexaazaꢀ1, 12ꢀdiborapentaꢀ
2
7
SHELXTL PLUS program package. The positions of the disꢀ
ordered atoms were revealed from difference Fourier syntheses.