534
Inorg. Chem. 1996, 35, 534-536
Notes
Table 1. Crystallographic Data for 2
Palladium(II) Arenethiolates with Chelating
Diamines: Formation of N-H‚‚‚S Hydrogen
Bonds with Protonated
formula
space group
cryst system
Z
C24F20PdS4‚C6H18N2
C2/c (No. 15)
monoclinic
4
9.9905(6)
N,N,N′,N′-Tetramethylethylenediamine
a, Å
b, Å
c, Å
18.8645(11)
19.2540(14)
90.399(5)
3628.6(4)
1.869
8.5
0.71073 (graphite monochromator)
298
0.047
0.046
Gerardus M. Kapteijn,† David M. Grove,†
Wilberth J. J. Smeets,‡ Huub Kooijman,‡
Anthony L. Spek,‡,§ and Gerard van Koten*,†
â, deg
V, Å3
D
µ
calcd, g cm-3
calcd, cm-1
Department of Metal-Mediated Synthesis, Debye Institute,
and Crystal and Structural Chemistry, Bijvoet Center for
Biomolecular Research, Utrecht University, Padualaan 8,
3584 CH Utrecht, The Netherlands
radiation (Mo KR), Å
T, K
RF
RwF
a
b
b
a RF ) ∑||Fo| - |Fc||/∑|Fo|. RwF ) [∑[w(Fo - Fc)2]/∑[w(Fo)2]]1/2
.
ReceiVed June 7, 1995
enediamine) were prepared according to the literature.5 1H NMR
(300.13 MHz) spectra were recorded on a Bruker AC 300 spectrometer
at ambient temperature in CD3CN obtained from ISOTEC Inc. Infrared
spectra (KBr disks) were recorded on a Perkin-Elmer 283 spectrometer.
Elemental analyses were carried out by Dornis and Kolbe, Mikroana-
lytisches Laboratorium, Mu¨lheim a.d. Ruhr, Germany.
Introduction
Recently, the formation of N-H‚‚‚S hydrogen bonds has
attracted attention in transition metal arenethiolate chemistry.1
Several model complexes, e.g. [FeII(SAr)4]2- 2a
,
[FeIII(Cys-
have been
[Pd(SC6F5)2(Et2NCH2CH2NEt2)] (1). To a stirred solution of [Pd-
(OC6H5)2(teeda)] (0.20 g, 0.43 mmol) in CH2Cl2 (10 mL) was added
pentafluorothiophenol (0.70 g, 3.5 mmol). The pure product was
obtained by diffusion of pentane into this solution. The resulting
needle-shaped deep-red crystals were washed with pentane (2 × 5 mL)
and dried in Vacuo. Yield: 0.28 g (95%). Mp: 166 °C dec. 1H NMR
S)4]-,2b [MoVO(SAr)4]-,3a and [NiII(SAr)4]2- 3b
,
studied in order to establish the influence of such bonds on M-S
coordination. Understanding the nature of N-H‚‚‚S bonds in
inorganic complexes is also important for biochemists to gain
insights into the function of enzymes on a molecular level.4
Here, we report the reaction of bidentate N-donor-ligated bis-
(aryloxo)palladium(II) complexes with an aromatic thiol; de-
pending upon the alkyl substitution in the tetraalkylethylene-
diamine ligand used, either a neutral bis(arenethiolato)-
palladium(II) diamine species or a tetrakis(arenethiolato)-
palladium(II) diprotonated diamine species is formed. The latter
complex is the first example of a hydrogen-bonded “bridging”
[Me2(H)NCH2CH2N(H)Me2]2+ ligand, and this paper describes
the influence of N-H‚‚‚S hydrogen bonding on the square-
planar coordination geometry of the Pd(SC6F5)4 dianion.
2
3
(CD3CN): δ 3.20 (dq, 4H, CHaHbMe, Ja,b ) 13 Hz, Ja,Me ) 7 Hz),
2
3
3.01 (dq, 4H, CHaHbMe, Ja,b ) 13 Hz, Jb,Me ) 7 Hz), 2.86 (s, 4H,
N(CH2)2N), 1.40 (t, 12H, CH3). Anal. Calcd for C22H24F10N2S2Pd:
C, 39.03; H, 3.57; N, 4.14. Found: C, 38.74; H, 3.75; N, 4.08.
[Pd(SC6F5)4][Me2(H)NCH2CH2N(H)Me2] (2). To a stirred solution
of [Pd(OC6H5)2(tmeda)] (0.20 g, 0.49 mmol) or a solution of [Pd-
(OC6F5)2(tmeda)] (0.29 g, 0.49 mmol) in CH2Cl2 (10 mL) was added
pentafluorothiophenol (0.80 g, 4.0 mmol). After 1 min the dark red
solution was filtered. The pure product was obtained by diffusion of
pentane into this solution. The resulting block-shaped red crystals
(suitable for X-ray diffraction) were washed with pentane (3 × 10 mL)
and dried in Vacuo. Yield: 0.49 g (97%). Mp: 185 °C dec. 1H NMR
(CD3CN): δ 2.84 (s, 4H, NCH2), 2.72 (s, 12H, NCH3), 2.69 (br s, 2H,
NH). IR(KBr): νN-H 3250 cm-1. UV-vis (CD3CN): abs. (ꢀ (L mol-1
cm-1)): 24 300 (4100, d-d), 37 500 (49 200, MLCT), 49 500 (34 200,
MLCT) cm-1. Anal. Calcd for C30H18F20N2S4Pd: C, 35.29; H, 1.78;
N, 2.74. Found: C, 35.02; H, 2.07; N, 3.19.
Experimental Section
General Considerations. Pentafluorothiophenol was purchased
from Aldrich Chemical Co. and used as received. The complexes [Pd-
(OC6X5)2(tmeda)] (tmeda ) N,N,N′,N′-tetramethylethylenediamine; X
) H, F) and [Pd(OC6H5)2(teeda)] (teeda ) N,N,N′,N′-tetraethylethyl-
Crystal Structure Determination of 2. A dark red block-shaped
crystal was glued to the tip of a glass fiber and transferred to an Enraf-
Nonius CAD4-Turbo diffractometer with rotating anode. Lattice
parameters were determined by least-squares treatment, using the setting
angles (SET4) of 25 reflections in the range 10.0° < θ < 13.7°. The
unit cell parameters were checked for the presence of higher lattice
symmetry.6 Crystal data and details on data collection and refinement
are given in Table 1. Data were collected at ambient temperature in
ω/2θ mode with scan angle ∆ω ) 0.63 + 0.35 tan θ. Intensity data
of 4667 reflections were collected in the range 1.06° < θ < 27.50°, of
which 4159 are independent. A total of 2222 reflections with intensities
above 2.5σ(I) were used in the structure analysis. Data were corrected
for Lorentz-polarization effects and for a linear decay of 3% of the
three periodically measured reference reflections (2h25h, 225, 4h42) during
11 h of X-ray exposure time. The structure was solved by automated
* To whom correspondence should be addressed.
† Debye Institute.
‡ Bijvoet Center for Biomolecular Research.
§ Address correspondence regarding the crystallography to this author.
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J.; Dewan, J. C.; Walters, M. A. Inorg. Chim. Acta 1995, 228, 199.
(c) Huang, J.; Ostrander, R. L.; Rheingold, A. L.; Walters, M. A. Inorg.
Chem. 1995, 34, 1090.
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Commun. 1992, 1019. (b) Maelia, L. E.; Millar, M.; Koch, S. A. Inorg.
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(5) (a) Kapteijn, G. M.; Grove, D. M.; Smeets, W. J. J.; Spek, A. L.; van
Koten, G. Inorg. Chim. Acta 1993, 207, 131. (b) Hunter, C. A.; Lu,
X.-J.; Kapteijn, G. M.; van Koten, G. J. Chem. Soc., Faraday Trans.
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0020-1669/96/1335-0534$12.00/0 © 1996 American Chemical Society