W.-F. Liaw et al.
sis calcd (%) for C60H46FeN5O2P2: C 73.03, H 4.70, N 7.10; found: C
the solution of DMF and complex 4 layered with diethyl ether and
hexane at À208C for 4 d.
73.43, H 5.00, N 7.90. The 15N-labeled complex 1 was prepared in the
same manner by reaction of complex [PPN]ACHTNUTRGENNUG ACHUTNTGNER(NGUN SC7H4SN)2] and
[(15NO)2Fe
potassium carbazolate (2 equiv). IR (THF): n˜ =1714 (s), 1657 cmÀ1 (s;
Reaction of P(SH)3 (P(SH)3 =P(C6H3-3-SiMe3-2-SH)3) and 1: THF
(3 mL) was added through a gas-tight syringe to a 30 mL Schlenk flask
15NO).
loaded with complex
1 (0.198 g, 0.2 mmol) and P(SH)3 (0.115 g,
0.2 mmol) at 08C. The reaction solution was monitored by FTIR. The IR
nNO shifted from (1748 (s), 1691 (s)) to (1682 (s), 1638 cmÀ1 (s)) when the
reaction solution was stirred for 10 min. The IR nNO further shifted to
1720 cmÀ1 after the reaction solution was stirred for another 20 min at
Reaction of bis(dimethylthiocarbamoyl) disulfide (DTC) and 1: Bis(di-
methylthiocarbamoyl) disulfide (DTC; 0.048 g, 0.2 mmol) and complex 1
(0.198 g, 0.2 mmol) were dissolved in THF (5 mL) and stirred for 4 h at
ambient temperature under an N2 atmosphere. The IR nNO spectrum
showed a strong absorption band at 1715 cmÀ1 (THF) assigned to the for-
mation of the known complex [(NO)Fe
in THF was filtered through Celite to remove the insoluble [PPN]-
[C12H8N] solid characterized by 1H NMR spectroscopy ([D6]DMSO): d=
ACHTUNGTRENNUNG
ambient temperature. The IR stretching frequency located at 2223 cmÀ1
,
(S2CNMe2)2] (2).[23] The solution
ACHTUNGTRENNUNG
assigned to the formation of N2O, was observed. Hexane was then added
to lead to the precipitation of the dark green solid [PPN][Fe(PS3)(NO)]
AHCTUNGTRENNUNG
(5) (yield 0.210 g, 88%) characterized by IR, UV/Vis, and single-crystal
X-ray diffraction. The carbazole by-product that was dissolving in the
THF/hexane solution was isolated and characterized by 1H NMR spec-
troscopy. Recrystallization from THF solution of complex 5 layered with
hexane at À208C for 4 d led to the dark green crystals suitable for X-ray
crystallography. Complex 5: IR (THF): n˜ =1720 cmÀ1 (NO); UV/Vis
(THF): lmax (e)=526 (1800), 579 nm (2000 molÀ1 dm3 cmÀ1); elemental
analysis calcd (%) for C63H66FeN2OP3S3Si3: C 63.24, H 5.56, N 2.34;
found: C 63.02, H 4.98, N 2.77.
8.04 (d), 7.79 (m), 7.46 (m), 7.30 (t), 7.05 ppm (t). Addition of hexane
(20 mL) to the filtrate (THF) led to the precipitation of green solid
[(NO)FeACHTUNGTRENNUNG(S2CNMe2)2] (2) (yield 0.058 g, 89%). The upper-layer THF/
hexane solution was transferred to the another flask through a stainless
steel cannula and dried under vacuum to obtain N-nitrosocarbazole (3).
Compound 3 was redissolved in hexane and kept in the refrigerator at
À208C for 2 d. Pale-yellow crystals suitable for X-ray diffraction analysis
were obtained (0.016 g, 42%). Compound 3: 1H NMR (500 MHz,
[D6]DMSO, TMS): d=8.43 (d), 8.21 (d), 8.16 (m), 7.61 (t), 7.56 ppm (m);
15N NMR (500 MHz, [D6]DMSO, nitromethane): d=170 ppm (s); IR
(KBr): n˜ =1491 cmÀ1 (s) (NO); UV/Vis (THF): lmax (e)=281 (11200),
331 (9920), 414 (300), 434 nm (200 molÀ1 dm3 cmÀ1); elemental analysis
calcd (%) for C13H12N2O: C 73.56, H 5.70, N 13.20; found: C 73.46, H
6.36, N 13.70. The 15N-labeled compound 3 was prepared in the same
Reaction of P
N
CATHNUGTRNEUN(NG SNa)3 =P(C6H3-3-SiMe3-2-SNa)3) and complex
1: Compounds PACHTUNGTRENNUNG
were dissolved in THF (3 mL) and stirred under N2 at 08C for 5 min. The
reaction was monitored with FTIR, and the IR nNO shifting from (1748
(s), 1691 (s)) to 1720 cmÀ1 (s) implied the formation of complex 5. A so-
lution of THF (3 mL) and [PPN]ACHTUNRTGENNUG ACHTUNGTREN(NUGN SPh)3] was immediately
[(15NO)Fe
manner by reaction of complex [PPN]
(1 equiv). IR (KBr): n˜ =1462 cmÀ1(s; 15NO).
[(15NO)2Fe
ACHTUGTNRENNUG AHCTUNGTREN(NGUN C12H8N)2] and DTC
added to the mixture solution and monitored with FTIR. The appearance
AHCTUNGTRENNUNG
of IR nNO stretching frequencies at 1732 (sh), 1693 (s), and 1670 cmÀ1 (s)
was assigned to the formation of [PPN]
parable to the authentic complex [PPN]
[(15NO)
by reaction of [PPN]
[(15NO)Fe(SPh)3] and 14NO(g) (1 equiv). The mixture
solution was filtered through Celite to remove the insoluble [PPN]-
[C12H8N] solid characterized by 1H NMR spectroscopy. The addition of
diethyl ether (6 mL) to the solution in THF led to the precipitation of
the insoluble [PPN]
[SPh] solid characterized by 1H NMR spectroscopy.
A
(14NO)Fe
ACHUTGTNRENNUG CAHTUNGTRENNUNG
Reaction of compound 3 and N-acetylpenicillamine (NAP): [D6]DMSO
(1 mL) was added to a 30 mL Schlenk flask loaded with compound 3
(0.099 g, 0.5 mmol) and N-acetylpenicillamine (NAP; 0.096 g, 0.5 mmol).
The reaction solution was stirred at ambient temperature for 8 h and
monitored with 15N NMR spectroscopy. The disappearance of the
15N NMR chemical shift at d=170 ppm and the appearance of the chemi-
cal shift at d=447 ppm were observed. THF (1 mL) and diethyl ether
(20 mL) were then added to the solution in [D6]DMSO, thus leading to
the precipitation of the known green solid S-nitroso-N-acetylpenicilla-
mine (SNAP; 0.099 g, 90%).[10b,c] The solution in [D6]DMSO/THF/diethyl
ether was then transferred into another flask through a stainless steel
cannula under positive nitrogen pressure and dried under vacuum to
obtain carbazole as identified by 1H NMR spectroscopy ([D6]DMSO):
d=11.23 (s), 8.09 (d), 7.48 (d), 7.37 (m), 7.15 ppm (m).
A
R
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
More diethyl ether (6 mL) was added to the solution in THF/diethyl
ether to separate the insoluble complex 5 (0.016 g, 67%), characterized
by IR and UV/Vis, and the upper solution. The upper solution was then
dried under vacuum to yield the brown solid [PPN]
(SPh)2] (0.007 g, 42%) characterized by IR and UV/Vis spectroscopy.[26]
[(15NO)(14NO)Fe-
ACHUTGTNRENNUG ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
EPR measurements: X-band EPR measurements were performed using
a Bruker EMX spectrometer equipped with a Bruker TE102 cavity. The
microwave frequency was measured with a Hewlett–Packard 5246L elec-
tronic counter. X-band EPR spectra of complex 1 frozen in THF were
obtained with a microwave power of 19.971 mW, frequency at 9.483 GHz,
and modulation amplitude of 0.1 G at 100 KHz.
Reaction of (PyPepS)2 ACHTUNGTRENNUNG(PyPepS=[SC6H4-o-NHC(O)HCAUTNGTREN(NUGN C5H4N)]2) and 1: A
solution of THF (5 mL) and complex 1 (0.198 g, 0.2 mmol) was prepared
under an N2 atmosphere in a vial. The vial containing the solution of 1 in
THF was then placed in a larger vial containing a solution of [PPN]2-
ACHTUNGTRENNUNG[S5FeACHTUNGTRENNUNG(m-S)2FeS5] in THF/CH3CN (0.157 g, 0.1 mmol) and the large vial
Crystallography: The crystals of complexes 1, 3, 4, and 5 chosen for X-
ray diffraction studies measured 0.28ꢄ0.18ꢄ0.07, 0.56ꢄ0.30ꢄ0.11, 0.45ꢄ
0.36ꢄ0.24, and 0.29ꢄ0.23ꢄ0.12 mm in size, respectively. Each crystal was
mounted on a glass fiber and quickly coated in epoxy resin. Unit-cell pa-
rameters were obtained by least-squares refinement. Diffraction meas-
urements for complexes 1, 3, 4, and 5 were carried out using a SMART
Apex CCD diffractometer with graphite-monochromated MoKa radiation
(l=0.7107 ꢂ) and between 2.03 and 25.028 for complex 1, between 1.20
and 25.038 for complex 3, between 1.69 and 25.038 for complex 4, and be-
tween 2.18 and 24.988 for complex 5. Disorder of N(4)/N(4’) atoms and
O(2)/O(2’) atoms of compound 3 was observed with equal occupancy fac-
tors of 50%. Disorder of O(1) and O(1’) atoms of complex 5 was ob-
served with equal occupancy factors of 50%. Least-squares refinement of
the positional and anisotropic thermal parameters of all non-hydrogen
atoms and fixed hydrogen atoms were based on F2. A SADABS[31] ab-
sorption correction was made. The SHELXTL[32] structure refinement
program was employed.
was capped with a well-sealed septum. A solution of N-2-mercaptophen-
yl-2’-pyridinecarboxamide disulfide ((PyPepS)2) (0.2 mmol, 0.092 g) in
THF (5 mL) was then added into the vial containing the solution of 1 in
THF by using a gas-tight syringe. The mixture solution was stirred at am-
bient temperature for 8 h. The resulting solution kept in the larger vial
was transferred to another tube and dried under vacuum. The crude solid
was redissolved in THF and filtered through Celite to remove the insolu-
ble solid. Addition of hexane to the filtrate led to the precipitation of the
known complex [PPN]ACHTUNGTRENNUNG[S5Fe(NO)2] (0.044 g, 27%) characterized by IR
spectroscopy.[24] In the meantime, hexane (20 mL) was added to the
brown reaction solution kept in the small vial to result in the precipita-
tion of the insoluble brown solid [PPN][FeACTHNUTRGNEG(NU PyPepS)2] (4) (0.177 g, 84%)
characterized by IR (nCO =1677 cmÀ1 (s) (CH3CN)) and UV/Vis (438,
520, 880 nm (DMF)). The upper solution (THF/hexane) was dried under
vacuum to obtain carbazole as characterized by 1H NMR spectroscopy.
Brown crystals suitable for X-ray diffraction analysis were isolated from
8094
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2010, 16, 8088 – 8095