Vinny Mehra et al.
CCDC number: 784651 or 1 (Fax: +44-1223-336-033;
(i)
O2
NH
2 HN
HN
N
N
NH
Acknowledgements
O
(thione)
S
S
S
One of us (AKB) thanks the – Indian Academy of Sciences
(Bangalore), National Academy of Sciences (Allahabad) and
Indian National Science Academy (New Delhi) for a Sum-
mer Fellowship. Financial assistance from the Council of
Scientific and Industrial Research (CSIR), New Delhi, in the
form of Emeritus Scientist Grant [21(0904)/12-EMR-II] to
T.S. Lobana, is gratefully acknowledged.
N
N
N
N
(i)
1
O
(thiol)
SH
SH
References
Scheme 2. (i) PdCl2(PPh3)2, Et3N.
1. Raper E S 1996 Complexes of heterocyclic thion-
ates.1. Complexes of monodentate and chelating ligands
Coord. Chem. Rev. 153 199
Proton NMR spectrum of compound 1 in CDCl3
did not show –NH signal (cf: ligand, NH signal, δ =
6.40 ppm) and it confirmed deprotonation of NH pro-
tons. The –CH2– protons showed a broad signal at δ,
3.67 ppm, a lower field relative to the free ligand at
3.59 ppm. The P–Ph protons showed a multiplet in
the range, 7.46–7.67 ppm. The presence of CH3CN
was confirmed as a characteristic signal occurring at
2.18 ppm. Further, the 31P NMR spectrum showed a
signal at δ, 30.0 ppm with coordination shift (δcomplex
ligand) of 34.7 ppm.
The ESI-mass spectrum of compound 1 has shown
a signal at m/z = 585.03 (calcd m/z = 585.02) which
supports the formation of molecular species, [Pd{η3–S,
O, S–(SC3H4N2–O–N2C3H4S)}(PPh3)+H]+, chemical
formula C24H24N4OPPdS2, (Figure 2). The isotopic pat-
tern, observed and calculated, confirm the formation of
molecular ion species. Scheme 2 depicts the probable
pathway for the formation of compound 1.
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1992 Synthesis and solution behavior of mononuclear
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−
δ
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4. Conclusions
Complex [Pd{κ3–S, O, S–(SC3H4N2–O–N2C3H4S)}
(PPh3)]· CH3CN 1 emerged from in situ transforma-
tion of 1,3-imidazolidine-2-thione into a new thiolate
dianion, (SC3H4N2–O–N2C3H4S)2−. This is an unusual
reaction in synthetic inorganic chemistry, and may play
an important role in the heterocyclic chemistry by easily
combining imino groups.
8. Lobana T S, Sultana R, Hundal G and Castineiras A
2009 Synthesis and crystal structures of polynuclear
complexes of CuI with 1-methyl-1, 3-imidazoline-2-
thione Polyhedron 28 1573
Supplementary Information (SI)
9. Lobana T S, Kaur P J, Castineiras A, Turner P and
Failes T W 2008 Synthesis, crystal and molecular struc-
tures of isomorphic N, S-bridged [Cu2(μ2–I)2(PPh3)2
(μ2–N,S–pymSH)] dimer and S-bonded [CuX(η1–S–
pymSH)(PPh3)2] monomers (X = Cl, Br) Struct. Chem.
19 727
Crystallographic data (excluding structure factors) for the
structure in this paper have been deposited with the Cam-
bridge Crystallographic Data Centre, CCDC, 12 Union
Road, Cambridge CB21EZ, UK. Copies of the data can be
obtained free of charge on quoting the depository numbers