FULL PAPER

DOI:10.1002/ejic.201301054

Air-Stable and Volatile Bis(pyridylalkenolato)

germanium(II), -tin(II), and -lead(II) Complexes

Tim Heidemann[a] and Sanjay Mathur*[a]

Keywords: Main group metals / Lead / Tin / Germanium / N,O ligands / Molecular precursor

Homoleptic germanium(II), tin(II), and lead(II) complexes of gonal bipyramidal geometry for all three molecular struc-
the general formula M(2-PyCHCOCF3)2 (M = Ge, Sn, Pb; Py tures; this distortion is highest for the lead compound, prob-
= pyridine) were synthesized by treating the corresponding ably as a result of the high s character of the lone pair of
silyl amides [M{N(SiMe3)2}2] with two equivalents of a 3,3,3- electrons present on the metal centers. The monomeric na-
trifluoro-1-(2-pyridyl)prop-1-en-2-ol (2-PyCHCOHCF3) li- ture of the compounds in solution was confirmed by multinu-
gand. Single-crystal X-ray diffraction revealed the bidentate clear NMR spectroscopy, whereas a polymeric structure is
chelation of 2-PyCHCOHCF3, which imposes a distorted tri- observed for the lead complex in the solid state.

Introduction chelating ligand and the stability of the resulting six-mem-

bered metallacycles also offers the possibility of inhibiting
Thin films of main group metal oxides are of importance oligomerization to enhance volatility and thermal stability,
because of their semiconductor, optoelectronic, and sensing as shown by Appel et al.[8] for precursors to niobium(V)
properties.[1–4] In this context, the availability of suitable or- oxide. The motivation of this work was to synthesize new
ganometallic precursors is in the focus of recent research germanium(II), tin(II), and lead(II) compounds with prom-
trends dedicated to chemical materials synthesis.[5–9] ising properties for CVD application and investigate their
Among precursors to metal oxides, derivatives containing a structure in solution and the solid state. In contrast to met-
metal–oxygen bond such as alkoxides, β-diketonates, and allic phases obtained from late-transition metals such as
allied derivatives modified with chelate ligands are highly palladium and platinum, thermal conversion for oxophilic
preferred. For a large number of elements, the correspond- metals is expected to produce metal oxides.
ing metal–β-diketonates have been reported;[10,11] however,
they generally require a high temperature to be used in gas-
phase synthesis owing to strong metal–oxygen bonds, and
this leads to carbon residues in chemical vapor deposition
(CVD). The first synthesis of volatile lead–β-diketonates
was described by Schweitzer et al.,[12] whereas the equiva-
lent tin complex was first synthesized by Bos et al.[13] and
the more volatile fluorinated derivatives were reported by
Ewings et al.[14] The synthesis of germanium–β-diketonates
was briefly described by Rodgers et al.[15] The 2-
PyCHCOHCF3 ligand (Scheme 1) described by McGrath
et al.[16] is a promising alternative, because it shows superior
physicochemical properties than β-diketones, for example,
higher chemical and thermal stability and, therefore, in- Scheme 1. Synthesis of complexes 1–3.
creased volatility[7–9] (Figure 1). The first mention of β-alk-
enolate complexes in the context of CVD precursors was
given by Brückmann et al.[7] with the synthesis of volatile
palladium and platinum derivatives. The interplay of the

[a] Chair of Inorganic and Materials Chemistry, Institute of

Inorganic Chemistry, University of Cologne,
Greinstraße 6, 50939 Köln, Germany
E-mail: [email protected] Figure 1. Interplay of an electron-donating heterosubstituted aro-
http://mathur.uni-koeln.de/ matic ring (push) and an electron-withdrawing CF3 group (pull) to
Supporting information for this article is available on the achieve strong chelation of the metal center, which enables good
WWW under http://dx.doi.org/10.1002/ejic.201301054. volatility and stability.

Eur. J. Inorg. Chem. 2014, 506–510 506 © 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Results and Discussion

The divalent compounds of general formula M(2-
PyCHCOCF3)2 {M = Ge (1), Sn (2), Pb (3)} were synthe-
sized by deprotonation of 2-PyCHCOHCF3 (2 equiv.) with
the corresponding bisamides M[N(SiMe3)2]2 {M = Ge (4),
Sn (5), Pb (6)} in toluene (Scheme 1). The M[N-
(SiMe3)2]2 compounds were prepared by salt elimination
from the chlorides and in situ lithiated HN(SiMe3)2
(HMDS), whereas 2-PyCHCOHCF3 was prepared follow-
ing the procedure described by Kawase et al.[17] All three
products showed high solubility in toluene and dichloro-
methane, however low solubility in ether and alcohols.
The 1H NMR spectroscopic data of 1–3 (see the Sup-
porting Information) recorded in [D6]benzene solutions at
room temperature showed the expected ABCD spin system
for the aromatic protons. Comparison of the 1H NMR
spectra of all the compounds revealed only small differences
in the chemical shifts. The biggest difference was found for
the H1 and H6 protons, which are affected the most be-
cause of the proximity to the metal center. The resonance
of the vinylic H6 proton was consistently shifted to higher
field (δ = 6.08, 5.93, and 5.70 ppm) in the sequence Ge ⬎
Sn ⬎ Pb. A doublet for H1 was found at δ = 8.25 ppm for
the germanium compound, whereas for the tin complex a
high-field shift (δ =8.07 ppm) is observed. In contrast, the
resonance was shifted to lower field for the lead compound
(δ =8.67 ppm). All eight carbon signals in the 13C NMR
spectra exhibited only marginal fluctuation in their chemi-
cal shifts. Similarly, the 19F NMR signals were observed in
the range expected for carboxylic moieties and are compar-
able with our previous investigations.[7–9] For the tin com-
pound, a 119Sn NMR signal was detected at δ = –604 ppm,
which is comparable to values found for other tin complexes
with chelating N,O ligands possessing a tin(II) center in a
pyramidal configuration.[18]
In the EI-MS spectra of 1–3, the molecular ion peaks
[m/z = 450 (for 1), 496 (for 2), 584 (for 3)] were found with
relative intensities of 25–32 %. The base peak was obtained
by the loss of one ligand. The ligand is detected at m/z =
189 (6–12 %) and is further fragmented by the loss of a tri-
fluoromethyl group and a following elimination of CO.
Single crystals of 1 were obtained by recrystallization in
toluene and dichloromethane for 2 and 3, respectively. The
molecular structures of 1–3 exhibited two independent mir-
ror-imaged molecules. Given that their structural param-
eters are almost identical, only the molecules containing
Ge1, Sn1, and Pb1 are discussed. Compound 1 crystallized
in the monoclinic P21/c space group and displayed distorted
trigonal bipyramidal geometry around the center (Fig-
ure 2). The oxygen atoms of the ligand occupy two equato-
rial positions, whereas the third is occupied by the lone pair Figure 2. Molecular structure of M(2-PyCHCOCF3)2 {M = Ge (1),
of electrons. The nitrogen atoms are located at the axial Sn (2), Pb (3)} with thermal ellipsoids drawn at the 30 % probability
positions. The angles are smaller than in an ideal trigonal level. All hydrogen atoms are omitted for clarity. Selected bond
bipyramid, because of the higher space requirement of the lengths [Å], angles, and torsion angles [°] in sequence Ge, Sn, Pb:
M1–O1 1.877(5), 2.108(18), 2.437(8); M1–N1 2.277(7), 2.43(2),
lone pair of electrons (N1–Ge–N1⬘, 156.7°; O1–Ge–O1⬘, 2.503(10); O1–M1–O1⬘ 95.84(18), 93.7(7), 143.7(2); N1–M1–N1⬘
95.8°). Compounds 2 and 3 are less symmetric and crys- 156.7(2), 147.1(6), 83.9(3); N1–M1–O1 85.2(2), 80.8(7), 74.3(3);
tallized in the triclinic P1̄ space group, but they still display N1–M1–O1⬘ 79.4(2), 77.7(7), 79.7(3).

Eur. J. Inorg. Chem. 2014, 506–510 507 © 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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a distorted trigonal bipyramidal molecular structure. Com-

pound 2 also shows the less-common pyramidal tetracoor-
dination of divalent tin (Figure 3, III).[19]

Figure 4. Comparison of angles between ligand planes (determi-

nation of planes by method of least-squares).

Figure 3. Structure motives of di-, tri-, and tetracoordinated tin(II)

compounds.

Distortion increased in the sequence 1 ⬍ 2 ⬍ 3 appar-

ently as a result of the bigger size and more diffused charac-
ter of the s orbitals. For compound 2, the effect is low with Figure 5. Crystal structures of 1 (I), 2 (II), and 3 (III) with unit
an N1–Sn–N1⬘ angle of 147.2° and an O1–Sn–O1 angle of cells and completed fragments viewed along the a axis.
93.8°, but the high degree of distortion in compound 3 led
to reversal of the atom positions. Thus, the N1–Pb–N1⬘ an-
gle is much smaller (83.9°) and the O1–Pb–O1⬘ angle is
highly increased (143.7°), whereby the nitrogen atoms oc-
cupy the equatorial positions and the oxygen atoms are
shifted to the axial positions in a trigonal bipyramidal ar-
rangement. The strong distortion also resulted in a less-
planar ligand with a dihedral angle (C5–C6–C7–C8) of
10.1°. The ligand bite angles (N1–M–O1) are gradually re-
duced in the sequence Ge ⬎ Sn ⬎ Pb (85.2, 80.9, 74.3°). The
M–O1 bond lengths (1.88, 2.11, 2.44 Å) and M–N1 bond
lengths (2.28, 2.43, 2.50 Å) increase as expected from the
Figure 6. Representation of the oxygen-bridged alignment of 3 in
electronic features and are in good agreement with the in- the crystal.
teratomic distances reported for comparable germanium,[20]
tin,[21,22] and lead[21,23,24] complexes with N,O-chelating li-
Conclusions
gands.
The overall distortion is also reflected in the comparison Air-stable and volatile germanium(II), tin(II), and
of the ligand plane angles (angle between averaged plane lead(II) heteroaryl alkenolate complexes were synthesized
N1–C1–C2–C3–C4–C5–C6–C7 and averaged plane N1⬘– and characterized extensively in solution and in the solid
C1⬘–C2⬘–C3⬘–C4⬘–C5⬘–C6⬘–C7⬘), which is decreased from state. The molecular structures showed distorted trigonal bi-
58.44 to 57.05 to 42.76° (Figure 4). The crystal packing of pyramidal geometry imposed by bidentate chelation of the
1–3 (Figure 5) shows how the molecules align their fluorine ligand unit, Py–CH–C(R)–OH (Py = pyridine, R = CF3),
atoms towards each other. The presence of high negative which was substantiated with increasing atomic size and
charge density in the organic periphery of the complexes largest for the lead compound. The volatility of these com-
coupled with the enhanced intermolecular repulsion con- pounds is explained by the strong chelation of the ligand
tributes to the enhanced volatilities of the complexes. This units and the cooperativity among the electron-back-donat-
aspect underscores the influence of steric and electronic fac- ing nitrogen atom and the electron-withdrawing influence
tors in the design of suitable metal–organic precursors with of the CF3 group, which results in effective steric shielding
desired physicochemical properties.[6a] of the metal atoms. As a result, the transposition of the
Figure 6 reveals the alignment of the molecules of 3 in nitrogen and oxygen atoms was reversed in the lead deriva-
oxygen-bridged chains with Pb2–O1 and Pb1–O2 distances tive, which showed strong intermolecular interactions in the
of 2.88 Å. The lead complex exhibits a unique distorted oc- solid state that were revealed in a polymeric structure. All
tahedral polymer structure unlike the structures found for three obtained compounds are highly stable to air and
1 and 2. The crystallographic data of the X-ray diffraction moisture, which in conjunction with their good vapor pres-
analysis of 1–3 are summarized in Table 1. sure indicates their suitability as precursors for metal oxides

Eur. J. Inorg. Chem. 2014, 506–510 508 © 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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through CVD processes. The application potential of these (25 mL) was stirred for 1 h. After removing the solvent, the product
compounds, especially the Ge and Sn compounds, in mate- was obtained as a yellowish solid, yield 2.01 g (4.48 mmol, 64 %;
rials synthesis is currently being investigated. m.p. 134 °C). Molar mass: 448.85 g mol–1. 1H NMR (C6D6): δ =
8.25 (d, J = 4.8 Hz, H1), 6.95 (t, J = 7.7 Hz, H3), 6.50 (t, J =
6.4 Hz, H2), 6.44 (d, J = 7.9 Hz, H4), 6.08 (s, H6) ppm. 13C NMR
(C6D6): δ = 151.7 (C5), 149.9 (C7), 144.6 (C1), 138.5 (C3), 123.2
Experimental Section (C4), 121.4 (C8), 121.0 (C2), 98.8 (C6) ppm. 19F NMR (C6D6): δ
General Procedures: All syntheses were performed under an inert = –73.1 ppm. MS (EI): m/z (%) = 450 (28) [M]+, 262 (100) [Ge(2-
nitrogen atmosphere by using a modified Stock glass vacuum line. PyCHCOCF3)]+, 189 (6) [2-PyCHCOHCF3]+, 120 (4) [2-PyCH-
The used solvents were dried with sodium and freshly distilled. The COH]+, 92 (3) [2-PyCH2]+. IR: ν̃ = 2964 (νC–H), 1600 (νC=C),
chlorides were dried with thionyl chloride. The organic ligand 2- 1442, 1403 (νC=N), 1283 (νC–F) cm–1. C16H10F6GeN2O2 (448.85):
PyCHCOHCF3 was synthesized according to previously described calcd. C 42.81, H 2.25, N 6.24; found C 42.19, H 1.99, N 6.26.
procedures.[17] The 1H NMR, 13C NMR, 19F NMR, and 119Sn Sublimation temperature: 100 °C, 10–3 mbar.
NMR spectra were recorded with a Bruker Avance II 300 spec- Sn[N(SiMe3)2]2 (5): HMDS (28.26 mL, 136.52 mmol) was cooled
trometer and are referenced to SiMe4 (1H, 300.0 MHz; 13C, to –196 °C and nBuLi (1.6 m in heptane, 85.33 mL, 136.52 mmol)
75.4 MHz), CCl3F (19F, 282.2 MHz), and SnMe4 (119Sn, was added. The mixture was stirred for 30 min while thawing and
111.8 MHz). Mass spectra were recorded with a Thermo Quest a solution of tin(II) chloride (12.94 g, 68.26 mmol) in THF (10 mL)
Finnigan MAT 95 with electron impact ionization at 20 eV. IR was added. After another 2 h of stirring, the solvent was removed
spectra were recorded with a Perkin–Elmer Spectrum 400 FTIR/ under reduced pressure. The crude product was purified at 75 °C
FTFIR spectrometer. Elemental analyses were performed with a by distillation in vacuo (2 ⫻ 10–2 mbar). The product was obtained
Hekatech CHNS EuroEA 3000 Analyzer. Melting points were de- as a red oil, yield 24.36 g (55.43 mmol, 81 %). Molar mass:
termined with a Stuart SMP10. X-ray crystallographic data 439.48 g mol–1. 1H NMR (C6D6): δ = 0.27 (s) ppm. 13C NMR
(Table 1) were collected by using a STOE IPDS I diffractometer (C6D6): δ = 5.9 ppm. 119Sn NMR (C6D6): δ = –604 ppm.
(Mo-Kα = 0.71073 Å, 50 kV, 30 mA). The programs used for struc-
ture solution and refinement include SIR-95,[25] SHELXS,[26] Sn(2-PyCHCOCF3)2 (2): Sn(2-PyCHCOCF3)2 was prepared analo-
SHELXL,[27] and WinGX.[28] gously to Ge(2-PyCHCOCF3)2 by reaction of Sn[N(SiMe3)2]2
(1.52 g, 3.45 mmol) and 2-PyCHCOHCF3 (1.30 g, 6.90 mmol) in
Table 1. Summary of crystallographic data for compounds 1–3. toluene. The resulting product was a yellowish solid, yield 0.91 g
(1.84 mmol, 53 %; m.p. 183 °C). Molar mass: 494.95 g mol–1. 1H
1 2 3
NMR (C6D6): δ = 8.07 (d, J = 5.0 Hz, H1), 6.91 (t, J = 7.7 Hz,
Formula C16H10N2O2F6Ge C16H10N2O2F6Sn C16H10N2O2F6Pb H3), 6.49 (t, J = 6.3 Hz; H2), 6.43 (d, J = 7.9 Hz, H4), 5.93 (s, H6)
M [g mol–1] 448.85 494.95 583.45 ppm. 13C NMR (C6D6): δ = 153.7 (C5), 152.7 (C7), 145.3 (C1),
Crystal system monoclinic triclinic triclinic 138.4 (C3), 123.7 (C4), 121.6 (C8), 120.4 (C2), 97.6 (C6) ppm. 19F
Space group P21/c P1̄ P1̄ NMR (C6D6): δ = –73.5 ppm. 119Sn NMR (C6D6): δ = –604 ppm.
a [Å] 8.82(1) 8.89(9) 8.15(6)
MS (EI): m/z (%) = 496 (32) [M]+, 308 (100) [Sn(2-PyCHCO-
b [Å] 11.15(9) 10.35(6) 10.21(5)
c [Å] 19.76(1) 10.85(5) 11.21(2) CF3)]+, 189 (6) [2-PyCHCOHCF3]+, 120 (5) [2-PyCHCOH]+, 92
α [°] 90 63.63(2) 99.92(7) (3) [2-PyCH2]+. IR: ν̃ = 2968 (νC–H), 1597 (νC=C), 1443, 1408
β [°] 114.93(1) 89.21(2) 99.40(2) (νC=N), 1270 (νC–F) cm–1. C16H10F6N2O2Sn (494.95): calcd. C
γ [°] 90 86.28(3) 107.99(2) 38.83, H 2.04, N 5.66; found C 39.18, H 1.95, N 5.51. Sublimation
V [Å3] 1763.8(6) 894.4(3) 851.5(3) temperature: 120 °C, 10–3 mbar.
Z 4 2 2
ρcalcd. [gcm–3] 1.69018 1.838 2.276 Pb[N(SiMe3)2]2 (6): HMDS (15.23 mL, 73.58 mmol) was cooled in
Reflections 15355 8034 10200 liquid nitrogen and nBuLi (1.6 m in heptane, 45.99 mL 73.58 mmol)
collected was added. The reaction mixture was warmed to room temperature
Indepentent 3095 2967 3800 and left to stir for 30 min. Afterwards, a solution of PbCl2 (10.23 g,
reflections 36.79 mmol) in THF (10 mL) was added. After 2 h of stirring, the
Observed 1428 1442 1379 solvent was removed under reduced pressure, and the crude prod-
reflections uct was distilled at 80 °C in vacuo (2 ⫻ 10–2 mbar). The product
GOF 0.731 1.091 0.882
was obtained as an orange yellow oil, which was used without fur-
R1, wR1 [I ⬎ 2σ(I)] 0.0469, 0.0758 0.1288, 0.3432 0.0500, 0.1001
ther analysis, yield 13.8 g (26.14 mmol, 71 %). Molar mass:
R1, wR1 (all data) 0.1601, 0.1001 0.1896, 0.3682 0.1036, 0.1159
527.97 g mol–1.
Pb(2-PyCHCOCF3)2 (3): Pb(2-PyCHCOCF3)2 was synthesized
Ge[N(SiMe3)2]2 (4): HMDS (15.15 mL, 73.22 mmol) was cooled in
analogously to Ge(2-PyCHCOCF3)2 and Sn(2-PyCHCOCF3)2 by
liquid nitrogen and covered with a layer of nBuLi (1.6 m in heptane,
a reaction of Pb[N(SiMe3)2]2 (2.26 g, 4.29 mmol) and 2-PyCH-
45.77 mL, 73.22 mmol). The mixture was stirred for 30 min while
COHCF3 (1.62 g, 8.58 mmol) in toluene. The obtained product was
thawing. Afterwards, a solution of GeCl2·dioxane (8.48 g,
a grey solid, yield 1.82 g (3.12 mmol, 73 %; m.p. 211 °C). Molar
36.61 mmol) in diethyl ether (40 mL) was added slowly. After 2 h
mass: 583.45 g mol–1. 1H NMR (C6D6): δ = 8.67 (d, J = 4.5 Hz,
of stirring, the solvent was removed under reduced pressure, and
H1), 6.80 (t, J = 7.5 Hz, H3), 6.48 (t, J = 6.2 Hz, H2), 6.30 (d, J
the crude product was distilled at 80 °C in vacuo (2 ⫻ 10–2 mbar).
= 8.1 Hz, H4), 5.70 (s, H6) ppm. 13C NMR (C6D6): δ = 156.4 (C5),
The resulting orange oil was used for the next step without further
152.9 (C7), 148.0 (C1), 137.0 (C3), 123.9 (C4), 122.8 (C8), 119.5
analysis, yield 8.23 g (20.92 mmol, 57 %). Molar mass:
(C2), 97.7 (C6) ppm. 19F NMR (C6D6): δ = –74.1 ppm. MS (EI)
393.41 g mol–1.
m/z (%): 584 (25) [M]+, 396 (100) [Pb(2-PyCHCOCF3)]+, 89 (12)
Ge(2-PyCHCOCF3)2 (1): A solution of Ge[N(SiMe3)2]2 (2.77 g, [2-PyCHCOHCF3]+, 120 (7) [2-PyCHCOH]+, 92 (4) [2-PyCH2]+.
7.03 mmol) and 2-PyCHCOHCF3 (2.66 g, 14.06 mmol) in toluene IR: ν̃ = 3059 (νC–H), 1597 (νC=C), 1446, 1405 (νC=N), 1273 (νC–

Eur. J. Inorg. Chem. 2014, 506–510 509 © 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 www.eurjic.org FULL PAPER

F) cm–1. C16H10F6N2O2Pb (583.46): calcd. C 32.94, H 1.73, N 4.80; [10] R. C. Mehrotra, R. Bohra, D. P. Gaur, Metal β-Diketonates and
found C 32.45, H 1.78, N 4.95. Sublimation temperature: 150 °C, Allied Derivatives, Academic Press, London 1978.
10–3 mbar. [11] S. Kawaguchi, Inorganic Chemistry Concepts: Variety in Coor-
dination Modes of Ligands in Metal Complexes, Springer,
CCDC-956137 (for 1), -956138 (for 3), and -956139 (for 2) contain Berlin, 1988.
the supplementary crystallographic data for this paper. These data [12] G. K. Schweitzer, B. P. Pullen, Y. H. Fang, Anal. Chim. Acta
1968, 43, 332.
can be obtained free of charge from The Cambridge Crystallo-
[13] K. D. Bos, H. A. Budding, E. J. Bulten, J. G. Noltes, Inorg.
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Nucl. Chem. Lett. 1973, 9, 961.
[14] P. F. R. Ewings, D. E. Fenton, P. G. Harrison, Inorg. Nucl.
Supporting Information (see footnote on the first page of this arti- Chem. Lett. 1974, 10, 43.
cle): NMR spectroscopic data and mass spectra. [15] A. Rodgers, S. R. Stobart, J. Chem. Soc., Chem. Commun.
1976, 52.
[16] T. F. McGrath, R. J. Levine, J. Am. Chem. Soc. 1955, 77, 3656.
Acknowledgments [17] M. Kawase, M. Teshima, S. Saito, S. Tani, Heterocycles 1998,
48, 2103.
[18] M. Schürmann, R. Schmiedgen, F. Huber, A. Silvestri, G. Ru-
The authors thank Dr. Wieland Tyrra for useful discussions and isi, A. B. Paulsen, R. J. Barbieri, J. Organomet. Chem. 1999,
Dr. Stefan Stucky for assistance with the X-ray crystal structure 584, 103.
determination. [19] T. Fjeldberg, P. B. Hitchcock, M. F. Lappert, S. J. Smith, A. J.
Thorne, J. Chem. Soc., Chem. Commun. 1985, 14, 939.
[20] S. Mahboob, M. Parvez, M. Mazhar, S. Ali, Acta Crystallogr.
[1] K. L. Choy, Prog. Mater. Sci. 2003, 48, 57. Sect. E Struct. Rep. Online 2005, 61, M358.
[2] M. N. Abbas, G. A. Moustafa, W. Gopel, Anal. Chim. Acta [21] M. C. Kuchta, J. M. Hahn, G. J. Parkin, J. Chem. Soc., Dalton
2001, 431, 181. Trans. 1999, 3559.
[3] J. Pan, R. Ganesan, H. Shen, S. Mathur, J. Phys. Chem. A [22] C. Kitamura, A. Yoneda, K. Sugiura, Y. Sakata, Acta Crys-
2010, 114, 8245. tallogr., Sect. C: Cryst. Struct. Commun. 1999, 55, 876.
[4] C. Goebbert, M. A. Aegerter, D. Burgard, R. Nass, H. J. [23] W. Starosta, J. Leciejewicz, Acta Crystallogr., Sect. E: Struct.
Schmidt, J. Mater. Chem. 1999, 9, 79. Rep. Online 2010, 66, M525.
[5] L. G. Hubert-Pfalzgraf, Inorg. Chem. Commun. 2003, 6, 102. [24] W. Starosta, J. Leciejewicz, Acta Crystallogr., Sect. E: Struct.
[6] a) S. Mathur, M. Driess, Comprehensive Organometallic Chem- Rep. Online 2010, 66, M192.
istry III, Elsevier, Amsterdam, The Netherlands, 2007, vol. 12; [25] A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi,
b) M. Veith, S. Mathur, C. Mathur, Polyhedron 1998, 17, 1005; M. C. Burla, G. Polidori, M. Camalli, J. Appl. Crystallogr.
c) R. C. Mehrotra, A. Singh, S. Sogani, Chem. Rev. 1994, 94, 1994, 27, 435.
1643. [26] G. M. Sheldrick, SHELXS-97, Program for the Solution of
[7] L. Brückmann, W. Tyrra, S. Stucky, S. Mathur, Inorg. Chem. Crystal Structures, University of Göttingen, Germany, 1997.
2012, 51, 536. [27] G. M. Sheldrick, SHELXL-97, Program for the Refinement of
[8] L. Appel, R. Fiz, W. Tyrra, S. Mathur, Dalton Trans. 2012, 41, Crystal Structures, University of Göttingen, Germany, 1997.
1981. [28] L. J. Farrugia, J. Appl. Crystallogr. 1999, 32, 837.
[9] I. Giebelhaus, R. Müller, W. Tyrra, I. Pantenburg, T. Fischer, Received: August 14, 2013
S. Mathur, Inorg. Chim. Acta 2011, 372, 340. Published Online: December 17, 2013

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