1-D networks formed by metal?sulfur van der Walls contacts: Novel tetrazole-thiolato Pd(II) and Pt(II) complexes

Article abstract of DOI:10.1016/j.inoche.2009.09.030

Pd(II)- and Pt(II)-azido complexes, [M(N₃)(PMe₃)₂(C-L)] {LH = 2-(2′)-thienyl pyridine; M = Pd (1), Pt(2)}, which contain σ-bonded heterocycles (L), were treated with aryl isothiocyanate (Me₂C₆H₃-NCS) to afford the corresponding Pd(II) and Pt(II) tetrazole-thiolato complexes, trans-{M[SCN₄(2,6-Me₂C₆H₃)]( PMe₃)₂(C-L)} {M = Pd (3), Pt (4)}. Complexes 3 and 4 have a 1-D helical network formed by the intermolecular M?S van der Waals contacts.

Full text of DOI:10.1016/j.inoche.2009.09.030

Inorganic Chemistry Communications 12 (2009) 1234–1237
Contents lists available at ScienceDirect
Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
1-D networks formed by metalꢀ ꢀ ꢀsulfur van der Walls contacts:
Novel tetrazole–thiolato Pd(II) and Pt(II) complexes
b
Hyeong-Tak Jeon a, Kyung-Eun Lee a,b, Yong-Joo Kim a, , Soon W. Lee
*
a Department of Chemistry, Kangnung National University, Gangneung 210-702, Republic of Korea
b Department of Chemistry, Sungkyunkwan University, Natural Science Campus, Suwon 440-746, Republic of Korea
a r t i c l e i n f o
a b s t r a c t
Pd(II)– and Pt(II)–azido complexes, [M(N3)(PMe3)2(C–L)] {LH = 2-(20)-thienyl pyridine; M = Pd (1), Pt(2)},
which contain r-bonded heterocycles (L), were treated with aryl isothiocyanate (Me2C6H3–NCS) to afford
Article history:
Received 9 July 2009
Accepted 28 September 2009
Available online 1 October 2009
the corresponding Pd(II) and Pt(II) tetrazole–thiolato complexes, trans-{M[SCN4(2,6-Me2C6H3)]-
(PMe3)2(C–L)} {M = Pd (3), Pt (4)}. Complexes 3 and 4 have a 1-D helical network formed by the intermo-
lecular Mꢀ ꢀ ꢀS van der Waals contacts.
Keywords:
Azido
Ó 2009 Elsevier B.V. All rights reserved.
Tetrazole–thiolato
Van der Waals interactions
Palladium: platinum
Thiophene compounds with extended
been intensively studied because of their potential usefulness in
the construction of self-assembled compounds and electronic or
p
-electron bonds have
strong N3 stretch at 2032–2042 cm–1, which are absent in com-
plexes 3 and 4. A singlet of the 31P{1H} spectra of the complexes
1–4 supports their trans-square-planar geometry.
chemical devices [1–8]. In particular, (
a
-position)-pyridyl-substi-
Complexes 3 and 4 were determined by X-ray diffraction [30].
The molecular structure of complex 3 with the atom-numbering
scheme is shown in Fig. 1a. The coordination sphere of Pd can be
described as square-planar. The molecular plane (P1, P2, S2, C1)
is nearly planar with an average atomic displacement of
0.017(1) Å, and the Pd metal lies 0.058(1) Å above this plane. The
Pd metal is further bound to the S atom in the neighboring mole-
cule by van der Waals contacts (Pdꢀ ꢀ ꢀS = 3.568(1) Å). These con-
tacts connect the molecules approximately along the b-axis to
give a 1-D helical network (Fig. 1b).
tuted thiophene derivatives exhibit interesting various coordina-
tion behaviors as well as electronic or electroluminescent
properties [9–23].
Recently, we reported the preparation of the pyridyl thienylene
complexes of group 10 metals [M(N3)L(C,N–L)], which contain C,N-
chelated ligands and azido groups [24,25]. The azido groups in
these complexes are photo-sensitive and undergo reactions with
organic unsaturated compounds to give heterocycles such as tetra-
zoles by the dipolar cycloaddition. In addition, the cyclometalated
complexes with C,N-donor ligands turned out to be labile toward
phosphines. In this paper, we report the preparation and structures
of tetrazole–thiolato Pd(II) and Pt(II).
The molecular structure of complex 4 is presented in Fig. 2a.
The molecular plane (P1, P2, S2, C1) of this square-planar complex
The starting complexes [M(
pyridine; M = Pd [25], Pt [26,27]), which were prepared from
[M( -Cl)(C,N-L)]2 and excess NaN3, were cleaved by excess PMe3
l
-N3)(C,N–L)]2 (LH = 2-(20)-thienyl
S
PMe
3
N
PMe
N3
N3
3
S
M
M
M
N3
l
N
S
M = Pd, 1
M = Pt, 2
to give the corresponding azido complexes [M(N3)(PMe3)2(C–L)]
{M = Pd (1), Pt (2)} [25,28], in which the original C,N–L ligand is
now a C-coordinated ligand (Scheme 1). Subsequent treatments
of complexes 1 and 2 with Me2C6H3–NCS afforded the correspond-
ing tetrazole–thiolato complexes, trans-{M[SCN4(2,6-Me2C6H3)]-
(PMe3)2(C–L)} {M = Pd (3), Pt (4)} [29], which have been formed
by the 1,3-dipolar cycloaddition of Ar–NCS into the metal–azido
bond (Scheme 1). The IR spectra of complexes 1 and 2 display a
PMe
3
N
PMe3
S
Ar-NCS
(Ar = 2,6-Me C H )
M
S
N
N
N
PMe3
2
6 3
N
N
M = Pd, 3
M = Pt, 4
* Corresponding author. Tel.: +82 33 640 2308; fax: +82 33 647 1183.
E-mail address: yjkim@kangnung.ac.kr (Y.-J. Kim).
Scheme 1.
1387-7003/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2009.09.030

H.-T. Jeon et al. / Inorganic Chemistry Communications 12 (2009) 1234–1237
1235
is also nearly planar with an average atomic displacement of
0.0255(8) Å, and the Pt metal lies 0.0539(8) Å above this plane.
The tetrazolato ring is significantly twisted from the phenyl ring
(C2–C7) by 76.8(1)°, probably due to the presence of the two
methyl groups at C3 and C9 atoms. In contrast, the thiophenyl
and pyridyl rings are essentially coplanar with a dihedral angle
of 2.0(1)°. As in complex 3, the Pt metal in complex 4 interacts with
the S atom in the neighboring molecule (Ptꢀ ꢀ ꢀS = 3.6018(8) Å) to
create a 1-D helical network along the b-axis. A space filling model
(Fig. 2b) clearly demonstrates the helical structure. For compari-
Fig. 1. (a) ORTEP drawing of 3 showing the atom-labelling scheme and 50% probability thermal ellipsoids. Selected bond lengths (Å) and angles (°): Pd1–C1 2.004(3), Pd1–P2
2.296(1), Pd1–P1 2.312(1), Pd1–S2 2.390(1), S2–C16 1.707(3), N2–N3 1.353(4), N3–N4 1.310(4), N4–N5 1.348(4), N5–C16 1.347(4); P2–Pd1–P1 173.71(4), P2–Pd1–S2
89.21(4), P1–Pd1–S2 95.79(4), C3–S1–C4 91.2(2), C16–S2–Pd1 103.3(1), C16–N2–N3 106.2(3), N4–N3–N2 111.2(3), N3–N4–N5 105.6(3), C16–N5–N4 109.2(3). (b) Projection
of complex 3 perpendicular to the (100) plane, showing a 1-D network approximately along the b-axis.

1236
H.-T. Jeon et al. / Inorganic Chemistry Communications 12 (2009) 1234–1237
Fig. 2. (a) ORTEP drawing of 4. Selected bond lengths (Å) and angles (°): Pt1–C18 2.015(3), Pt1–P1 2.2847(9), Pt1–P2 2.2960(8), Pt1–S1 2.3826(7), S1–C1 1.713(3), N1–N2
1.366(3), N2–N3 1.296(4), N3–N4 1.354(4), N1–C11.342(3); P1–Pt1–P2 174.99(3), P1–Pt1–S1 88.42(3), P2–Pt1–S1 94.59(3), C1–S1–Pt1 104.09(9), C16–S2–C19 91.49(16),
C1–N1–N2 108.4(2), N3–N2–N1 105.9(2), N2–N3–N4 111.4(2), C1–N4–N3 106.1(2). (b). A space filling model of the packing of complex 4 showing its helical structure: (a)
red, Pt; yellow, S; orange, P; purple, N; grey, C. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
son, the van der Waals radii of Pd, Pt, and S atoms are 1.63, 1.72,
and 1.80 Å, respectively. The van der Waals contacts (or
interactions) of metal–ligand and metal–metal types are known
to increase the dimensionality of coordination polymers or lead
to the formation of high-dimensional networks. Some recent
Acknowledgment
This work was supported by the Korea Research Foundation
Grant funded by the Korean Government (KRF-2008-313-C00452).
polymers and networks containing such contacts are [Cu4I4{l-
PhS(CH2)4SPh}2]n [33], {Fe(3-bromo-4-picoline)2[AuI(CN)2]2}n
References
[34], and especially silver species [35–40].
In summary, we prepared novel tetrazole–thiolato complexes,
trans-{M[SCN4(2,6-Me2C6H3)](PMe3)2(C–L)}
[1] D. Fichou (Ed.), Hand book of Oligo- and Polythiophenes, Wiley-VCH,
Weinheim, 1999;
(LH = 2-(20)-thienyl
D. Fichou, J. Mat. Chem. 3 (2000) 571.
pyridine; M = Pd, Pt) by treating the corresponding azido com-
plexes [M(N3)(PMe3)2(C–L)] with Me2C6H3–NCS. X-ray diffraction
studies revealed that these complexes have 1-D helical networks,
formed by the metalꢀ ꢀ ꢀsulfur van der Waals contacts.
[2] K. Mullen, G. Wegner (Eds.), ‘‘Oligothiophenes”, P. Bäuerle in Electronic
Materials: The Oligomer Approach, Wiley-VCH, Weinheim, 1998, pp. 105–197.
[3] J. Roncali, Chem. Rev. 92 (1992) 711.
[4] J.M. Tour, Acc. Chem. Res. 33 (2000) 791.
[5] R.A. Jones, P.U. Civcir, Tetrahedron 53 (1997) 11529.

H.-T. Jeon et al. / Inorganic Chemistry Communications 12 (2009) 1234–1237
1237
[6] M. Melucci, G. Barbarella, M. Zambianchi, P. Di Pietro, A. Bongini, J. Org. Chem.
69 (2004) 4821.
[7] R.D. Myrex, G.M. Gray, A.G. VanEngen Spivey, C.M. Lawson, Organometallics 25
(2006) 5045.
[8] H.-F. Lu, H.S.O. Chan, S.-C. Ng, Macromolecules 36 (2003) 1543.
[9] K.P. Balashev, M.V. Puzyk, V.S. Kotlyar, M.V. Kulikova, Coord. Chem. Rev. 159
(1997) 109.
[10] D.N. Kozhevnikov, V.N. Kozhenikov, M.M. Ustiniva, A. Santoro, D.W. Bruce, B.
Koenig, R. Czerwieniec, T. Fisher, M. Zabel, H. Yersin, Inorg. Chem. 48 (2009)
4179.
[11] W.M. Albers, G.W. Canters, J. Reedijk, Tetrahedron 51 (1995) 3895.
[12] L. Trouillet, A.D. Nicola, S. Guillerz, Chem. Mater. 12 (2000) 1611.
[13] (a) L. Chassot, A. von Zelewsky, Inorg. Chem. 26 (1987) 2814;
(b) H. Yersin, S. Schützenmeier, H. Wiedenhofer, A. von Zelewsky, J. Phys.
Chem. 97 (1993) 13496;
1H, J = 8.0 Hz, H6). 13C{1H} NMR (75 MHz, CDCl3, d): 13.2 (t, JCP = 7.5 Hz,
0
0
P(CH3)3), 119.1 (s, C3), 120.5 (s, C5), 126.3 (s, C5 ), 127.0 (s, C4 ), 135.8 (s, C4),
0
0
136.5 (s, C2 ), 149.2 (s, C3 ), 149.5 (br, C6), 155.6 (s, C2). 31P{1H} NMR (120 MHz
in CDCl3, d): –12.8 (s, JPtP = 2639 Hz). Anal. Calcd. for C15H24N4P2SPt: C, 32.79;
H, 4.40; N, 10.20. Found: C, 32.71; H, 4.52; N, 9.75.
5'
PMe3
4'
S
3'Pt N3
2'
2
PMe3
3
N
6
4
5
(c) A. von Zelewsky, A.P. Suckling, H. Stoeckli-Evans, Inorg. Chem. 32 (1993)
4585;
(d) P. Jolliet, M. Gianini, A. von Zelewsky, G. Bernardinelli, H. Stoeckli-Evans,
Inorg. Chem. 35 (1996) 4883;
(e) M. Gianini, A. Forster, P. Haag, A. von Zelewsky, H. Stoeckli-Evans, Inorg.
Chem. 35 (1996) 4889;
[29] Synthesis of trans-{M[SCN4 (2,6-Me2C6H3)](PMe3)2 (C–L)}(M = Pd, 3; Pt = 4):
To a Schlenk flask containing [Pd(N3)(PMe3)2 (C–L)] (1, 0.228 g, 0.50 mmol)
were added CH2Cl2 (4 ml) and 2,6-dimethylphenyl isothiocyanate (0.121 g,
0.74 mmol). After stirring for 18 h, the solvent was removed, and then the
resulting residue was solidified with n-hexane. The solids were filtered and
washed with hexane (5 ml ꢁ 2). Recrystallization from CH2Cl2/n-hexane gave
the white crystals of trans-{PdS[CN4(R)](C–L)(PMe3)2} (3, 0.141 g, 46%). 1H
(f) M. Gianini, A. von Zelewsky, H. Stoeckli-Evans, Inorg. Chem. 36 (1997) 6094.
[14] H. Yersin, D. Donges, W. Humbs, J. Strasser, R. Sitters, M. Glasbeek, Inorg.
Chem. 41 (2002) 4915.
[15] (a) T.J. Giordano, P.G. Rasmussen, 14 (1975) 1628.;
(b) T.J. Giordano, W.M. Butler, P.G. Rasmussen, 17 (1978) 1917.
[16] T. Janecki, J.A.D. Jeffreys, P.L. Pauson, A. Pietrzykowski, K.J. McCullough,
Organometallics 6 (1987) 1553.
NMR (CDCl3, d): 1.08 (br s, 18H, P(CH3)3), 2.07 (s, 6H, Me), 7.08 (d, 1H,
0
J = 5.0 Hz, H4 ), 7.10 (ddt, 1H, J = 1.1, 4.8, 9.8 Hz, H5), 07.21(d, 2H, J = 7.3 Hz, Ph),
7.32(t, 1H, J = 7.8 Hz, Ph), 7.39 (d, 1H, J = 4.6 Hz, H5 ), 7.92 (dt, 1H, J = 8.0 Hz,
H3), 8.54 (m, 1H, H4), 9.72 (br, 1H, H6). 13C{1H} NMR (CDCl3, d): 14.1 (t,
0
JPC = 14 Hz, P(CH3)3), 17.9 (s, Me), 120.5 (s, C3), 121.1 (s, C5), 126.6 (s, C5 ),
[17] A. Berger, J.-P. Djukic, M. Pfeffer, J. Lacour, L. Vial, A. de Cian, N. Kyritsakas-
Gruber, Organometallics 22 (2003) 5243.
0
0
128.5, 130.1,133.8, 134.2 (s, C4 ), 136.2, 137.1 (s, C4), 140.6 (s, C2 ), 146.8 (s,
C
0
3 ), 149.2 (s, C6), 155.0 (s, C2), 163.5). 31P{1H}NMR (CDCl3, d): –14.6 (s). Anal.
[18] J. Dupont, M. Pfeffer, J.C. Daran, Y. Jeannin, Organometallics 6 (1987) 899.
[19] (a) E.C. Constable, Y.A. Leese, J. Organomet. Chem. 363 (1989) 419;
(b) E.C. Constable, L.R. Sousa, J. Organomet. Chem. 427 (1992) 125;
(c) E.C. Constable, R.P.G. Henney, P.R. Raithby, L.R. Sousa, J. Chem. Soc. Dalton
Trans. (1992) 2251.
[20] J. Brooks, Y. Babayan, S. Lamansky, P.I. Djurovich, I. Tsyba, R. Bau, M.E.
Thomson, Inorg. Chem. 41 (2002) 3055.
[21] (a) S.-W. Lai, M.C.-W. Chan, K.-K. Cheung, S.-M. Peng, C.-M. Che,
Organometallics 18 (1999) 3991;
(b) S.-W. Lai, Q.K.-W. Chan, J. Han, Y.-G. Zhi, N. Zhu, C.-M. Che,
Organometallics 28 (2009) 34.
[22] N.M. Shavaleev, H. Adams, J. Best, R. Edge, S. Navaratnam, J.A. Weinstein, Inorg.
Chem. 45 (2006) 9410.
[23] J.-Y. Cho, B. Domercq, S. Barlow, K.Y. Suponitsky, J. Li, T.V. Timofeeva, S.C. Jones,
L.E. Hayden, A. Kimyonok, C.R. South, M. Weck, B. Kippelen, S.R. Marder,
Organometallics 26 (2007) 4816.
[24] (a) Y.-J. Kim, X. Chang, J.-T. Han, M.S. Lim, S.W. Lee, Dalton Trans. (2004) 3699;
(b) X. Chang, M.-Y. Kim, Y.-J. Kim, H.S. Huh, S.W. Lee, Dalton Trans. (2007) 792.
[25] K.-E. Lee, H.-T. Jeon, S.-Y. Han, J. Ham, Y.-J. Kim, S.W. Lee, Dalton Trans. (2009)
6578.
Calcd. for C24H33N5P2S2Pd: C, 46.19; H, 5.33; N, 11.22. Found: C, 46.15; H, 5.59;
N, 11.08. The complex, trans-{PtS[CN4(R)](C–L)(PMe3)2} (4, 0.162 g, 54%) was
analogously prepared. 1H NMR (CDCl3, d): 1.19 (t, J = 3.7, JPtH = 30 Hz, P(CH3)3),
2.06 (s, 6H, Me), 7.08–7.37(m, 6H, Ph), 7.91 (dt, 1H, J = 7.7 Hz, H3), 8.53 (m, 1H,
H4), 9.89 (br, 1H, H6). 13C{1H} NMR (CDCl3, d): 13.4 (t, JPC = 19 Hz, P(CH3)3), 17.8
0
(s, Me), 120.7 (s, C3), 121.2 (s, C5), 126.70 (s, C5 ), 128.5, 130.0,133.5, 136.0,
0
136.1, 136.8 (s, C4), 139.4 (t, JCP = 12 Hz, C3 ), 146.8 (s, C2 ), 148.9 (s, C6), 155.7
(s, C2), 161.2. 31P{1H}NMR (CDCl3, d): –16.9 (s, JPtP = 2575 Hz). Anal. Calcd.
for C24H33N5P2S2Pt: C, 40.45; H, 4.67; N, 9.83. Found: C, 40.25; H, 4.76;
N, 9.56.
[30] All X-ray data were collected with a Bruker Smart APEX2 diffractometer
equipped with a Mo X-ray tube. Collected data were corrected for absorption
with SADABS based upon the Laue symmetry by using equivalent reflections
[31]. All calculations were carried out with the use of SHELXTL programs [32].
Crystal data for 3: Mr = 624.01, colorless, monoclinic P21/c, a = 8.8658(2) Å,
b = 13.4779(3) Å, c = 24.3206(4) Å, b = 96.462(1) Å, V = 2887.7(1) Å3, Z = 4,
dcal = 1.435 g cm–3, crystal size = 0.40 ꢁ 0.38 ꢁ 0.34 mm3, F(000) = 1280, No.
of reflns measured = 42941, No. of reflns unique = 7202, No. of reflns with
I > 2r(I) = 4078, No. of params refined = 307, GOF = 1.003, R1 = 0.0416,
wR2 = 0.0807. Crystal data for 4: Mr = 712.70, colorless, monoclinic P21/c,
a = 8.88709(3) Å, b = 13.5076(4) Å, c = 24.3251(8) Å, b = 96.860(1) Å, V =
2893.8(2) Å3, Z = 4, dcal = 1.636 g cm–3, crystal size = 0.38 ꢁ 0.28 ꢁ 0.24 mm3,
F(000) = 1408, No. of reflns measured = 80741, No. of reflns unique = 6918, No.
of reflns with I > 2r(I) = 5109, No. of params refined = 295, GOF = 0.987,
R1 = 0.0242, wR2 = 0.0567.
[26] B.N. Cockburn, D.V. Howe, T. Keating, B.F.G. Johnson, J. Lewis, Dalton Trans.
(1973) 404.
[27] Synthesis of [Pt(
[Pt(N3)(PMe3)2(C–L)](2): To
[Pt( -Cl)(C,N-L)]2 (0.882 g, 1.13 mmol) was added a H2O (3 ml) solution of
l
-N3)(C,N-L)]2 (HC,N-L = 2-(20-thienyl)pyridine) and
a
homogeneous DMSO (100 ml) solution of
l
NaN3 (0.220 g, 3.38 mmol). After stirring for 18 h, excess H2O was added to the
mixture under ice bath to give dark yellow precipitates. The solids were
filtered and washed with H2O and diethyl ether. The product was dried under
[31] G.M. Sheldrick, SADABS, Program for Absorption Correction, University of
Göttingen, 1996.
[32] Bruker, SHELXTL, Structure Determination Software Programs, Bruker,
Analytical X-ray Instruments Inc., Madison, WI, USA, 1997.
[33] M. Knorr, F. Guyon, A. Khatyr, C. Däschlein, C. Strohmann, S.M. Aly, A.S. Abd-El-
Aziz, D. Fortin, P.D. Harvey, Dalton Trans. (2009) 948.
[34] T. Kosone, C. Kanadani, T. Saito, T. Kitazawa, Polyhedron 28 (2009) 1991.
[35] M.O. Awaleh, A. Badia, F. Brisse, Inorg. Chem. 44 (2005) 7833.
[36] Y. Qu, J. Wu, Acta Cryst. E63 (2007) m1063.
[37] H.S. Huh, S.H. Kim, S.Y. Yun, S.W. Lee, Polyhedron 27 (2008) 1229.
[38] S.H. Kim, S.W. Lee, Inorg. Chim. Acta 361 (2008) 137.
[39] H.S. Huh, S.Y. Yun, S.W. Lee, Bull. Korean Chem. Soc. 29 (2008) 1065.
[40] H.K. Lee, S.Y. Yun, S.W. Lee, Bull. Korean Chem. Soc. 28 (2007) 421.
vacuum to give brown solids of [Pt(
[28] To a Schlenk flask containing [Pt(
sequentially added CH2Cl2 (5 ml) and PMe3 (136
l
l
-N3)(C,N-L)]2 (0.819 g, 91%).
-N3)(C,N-L)]2 (0.304 g, 0.38 mmol) were
l, 1.53 mmol). The
l
heterogeneous brown solution immediately turned to an orange solution.
After stirring for 3 h at room temperature, the reaction mixture was
completely evaporated under vacuum to give dark yellow solids. The solids
were filtered and washed with hexane (5 ml). Recrystallization from CH2Cl2/
diethyl ether gave pale yellow crystals of 2 (0.332 g, 79%). IR (KBr, cm–1): 2042
(N3). 1H NMR(CDCl3 in 300 MHz, d): 1.26 (t, 18 H, J = 3.7, JPtH = 30 Hz, PMe3),
0
7.00 (d, 1H, J = 5.1 Hz, H4 ), 7.08 (ddt, 1H, J = 1.1, 4.9, 9.8 Hz, H5), 7.26 (d, 1H,
0
J = 4.9 Hz, H5 ), 7.66 (dt, 1H, J = 7.8 Hz, H3), 8.53 (d, 1H, J = 3.0 Hz, H4), 9.43 (d,