Synthesis, characterization and crystal structure of nickel complex (dppv)Ni(C7H4NS2)2

Article abstract of DOI:10.14233/ajchem.2014.15478

Reaction of 2-mercaptobenzothiazole with (dppv)NiCl2 (dppv: Ph2PCH=CHPPh2) in the presence of Et3N affords the title complex (dppv)Ni(C₇H ₄NS₂)2 in 92 % yield. The new complex was fully characterized by elemental analysis, TGA, IR and 1H (13C, 31P) NMR spectroscopies. In addition, the molecular structure of the title complex was established by X-ray crystallography. The crystal of (dppv)Ni(C ₇H₄NS₂)2?CH2Cl2 crystallizes in monoclinic, space group P2/n with a = 15.927(9), b = 8.3553(5), c = 16.3728(8) ?, a = 90.00, b = 112.417(4), g = 90.00°, V = 2014.22(19) ?3, Z = 2, C40H30N2NiP2S4?CH2Cl2, Mr = 872.48, Dc = 1.439 g/cm3, F(000) = 896 and μ(MoKa) = 0.934 mm-1. The final R = 0.0920 and wR = 0.2220 for 2572 observed reflections with I > 2s(I) and R = 0.1171 and wR = 0.2434 for all data. The geometry at the Ni centre in the title complex is square-planar with the NiP2S2 chromophore.

Full text of DOI:10.14233/ajchem.2014.15478

Asian Journal of Chemistry; Vol. 27, No. 4 (2015), 1555-1556
A
SIAN
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OURNAL OF HEMISTRY
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http://dx.doi.org/10.14233/ajchem.2015.17168
NOTE
Synthesis and Structural Characterization of Diiron
Azadithiolate Complex [(µ-SCH2)2NCH2CO2Me]Fe2(CO)4(CN-tert-Bu)2
*
HUI LI , QIAOJUAN GONG, XIAOCHUAN CHAI, CHENZHONG YAO and QIUPING HAN
Department of Applied Chemistry, Yuncheng University, Yuncheng 044000, Shanxi Province, P.R. China
*Corresponding author: E-mail: lihuiwangf@163.com
Received: 5 February 2014;
Accepted: 4 May 2014;
Published online: 4 February 2015;
AJC-16838
A diiron azadithiolate complex [(µ-SCH2)2NCH2CO2Me]Fe2(CO)4(CN-tert-Bu)2 (1), as the active site of [FeFe]-hydrogenases, has
been prepared by carbonyl substitution and structurally characterized. The title complex was prepared by reaction of
[(µ-SCH2)2NCH2CO2Me]Fe2(CO)6 (A) with tert-BuNC in CH2Cl2 in 46 % yield. The new complex was characterized by IR, 1H NMR and
13C NMR spectroscopy.
Keywords: Diiron azadithiolate, Isocyanide.
Over the past decades, research on iron-sulfur has attracted
great attention due to their close relationship with the active
site of [FeFe]-hydrogenases1-5. [FeFe]-hydrogenases are metallo-
enzymes which can catalyze hydrogen metabolism in several
microorganism6-8. The well-established structure of the active
site of [FeFe]-hydrogenases has provoked chemists to design
and prepared a great number of [FeFe]-hydrogenases model
complexes9-12. In this paper, we report the synthesis and struc-
tural characterization of diiron azadithiolate complex [(µ-
SCH2)2NCH2CO2Me]Fe2(CO)4(CN-tert-Bu)2 containing a iso-
cyanide ligand relevant to the active site of [FeFe]-hydrogenases.
Reaction and operation was carried out under a dry, oxygen
free nitrogen atmosphere with standard Schlenk and vacuum
line techniques. Dichloromethane was distilled with CaH2
under nitrogen atmosphere. Me3NO·2H2O, tert-BuNC and
other materials were commercially available and used as
received. Complex A13 was prepared according to the literature
procedures. IR spectra were recorded on a Nicolet 670 FTIR
spectrometer. NMR spectra were obtained on a BrukerAvance
500 MHz spectrometer.
red band afforded 0.056 g (46 %) of 1 as a red solid. IR (KBr
disk, cm-1): ν(C≡N) 2143 (s); ν(C≡O) 2002 (vs), 1968 (vs),
1951 (vs), 1928 (vs); ν(C=O) 1736 (s). 1H NMR (500 MHz,
CDCl3): 3.64, 3.61 (2s, 9 H, 3SCH2 and CH3), 1.45 (s, 18 H,
2C(CH3)3) ppm. 13C NMR (125 MHz, CDCl3): 213.53 (C≡O),
171.23 (C=O), 158.14 (NC), 57.44 (C(CH3)3), 57.16 (OCH3),
52.19 (NCH2S), 51.78 (NCH2), 30.83 (CH3) ppm.
As shown in Scheme-I, treatment of complex A with 2
equivelents of tert-BuNC in CH2Cl2 afforded the title complex
in 46 % yield. The title complex 1 was air-stable red solids,
which has been characterized by IR, 1H NMR and 13C NMR
spectroscopy.
NCH2CO2Me
NCH2CO2Me
S
S
S
S
tBuNC
CH2Cl2
CO
CO
OC
OC
Fe
Fe
Fe
Fe
OC
OC
OC
CO
CO
CO
CNBu
t
t
BuNC
1
A
Scheme-I: Synthesis of the title complex 1
Synthesis:A solution of [(µ-SCH2)2NCH2CO2Me]Fe2(CO)6
(0.100 g, 0.22 mmol) in MeCN (10 mL) was added a solution
of Me3NO·2H2O (0.024 g, 0.22 mmol) in MeCN (5 mL). The
mixture was stirred at room temperature for 15 min and then
was added tert-BuNC (0.048 mL, 0.44 mmol). The new mixture
was stirred for 1 h to give a red solution. The solvent was reduced
in vacuo and the residue was subjected to TLC separation using
CH2Cl2/petroleum ether (v/v = 1:2) as eluent. From the main
Infrared spectrum: The IR spectrum of 1 showed one
absorption band at 2143 cm-1 for isocyanide group, one
absorption band at 1736 cm-1 for ester carbonyls and four
absorption bands in the range of 2002-1828 cm-1 for the
terminal carbonyls and the ν(C≡O) values are shifted toward
lower frequencies relative to the parent complex A (2073, 2025,
1994, 1965 cm-1)13.

1556 Li et al.
Asian J. Chem.
1H NMR spectrum:The 1H NMR spectrum of 1 displayed
(c) X.F. Liu and H.Q. Gao, Polyhedron, 65, 1 (2013); (d) G. Durgaprasad,
R. Bolligarla and S.K. Das, J. Organomet. Chem., 706-707, 37 (2012);
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two singlets at δ 3.64 and 3.61 ppm for its methylene and
methyl protons and a singlet at d 1.45 ppm for methyl protons
of tert-Bu.
5. (a) P.H. Zhao, Y.F. Liu, K.K. Xiong and Y.Q. Liu, J. Clust. Sci., 25,
1061 (2014); (b) X.F. Liu, Z.Q. Jiang and Z.J. Jia, Polyhedron, 33, 166
(2012); (c) W.M. Gao and J.M. Li, Acta Crystallogr., E68, m118 (2012).
6. (a) L.J. Luo, X.F. Liu and H.Q. Gao, J. Coord. Chem., 66, 1077 (2013);
(b) X.F. Liu, M.Y. Chen and H.Q. Gao, J. Coord. Chem., 67, 57 (2014).
7. (a) Y.L. Li, B. Xie, L.K. Zou, X. Lin and L. Wang, Chinese J. Struct.
Chem., 32, 1105 (2013); (b) Y.L. Li, B. Xie, L.K. Zou, X. Lin and S.S.
Zhu, Z. Anorg. Allg. Chem., 639, 1011 (2013); (c)Y.L. Li, B. Xie, L.K.
Zou, X. Lin and S.S. Zhu, Asian J. Chem., 26, 183 (2014).
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13C NMR spectrum: The 13C NMR spectrum of 1
demonstrated a singlet at δ 213.53 ppm for the terminal
carbonyls, a singlet at δ 171.23 ppm for ester carbonyl and a
singlet at δ 158.14 ppm for isocyanide.
ACKNOWLEDGEMENTS
The authors gratefully acknowledge to the Natural Science
Foundations of China (51101138).
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and H.Q. Gao, J. Clust. Sci., 25, 495 (2014).
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