data reports
ISSN 2414-3146
Di-l-chlorido-bis({4-[bis(trimethylsilyl)amino]-6chloro-2,2,8,8-tetramethyl-5,7-bis(trimethylsilyl)3,5,7-triaza-4,6-diphospha-2,8-disilanon-3-en-4ido-j2P,P0 }palladium(II)) diethyl ether disolvate Martha Ho ¨ hne, Bernd H. Mu ¨ller, Anke Spannenberg and Uwe Rosenthal*
Received 4 June 2016 Accepted 17 June 2016
Edited by H. Ishida, Okayama University, Japan Keywords: crystal structure; dinuclear palladium complex; chloride-bridged complex; metal catalyzed coupling; phosphorous ligand. CCDC reference: 1486161 Structural data: full structural data are available from iucrdata.iucr.org
Leibniz-Institut fu¨r Katalyse e. V. an der Universita¨t Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany. *Correspondence e-mail:
[email protected]
The title compound, [Pd2(C18H54Cl2N4P2Si6)2Cl2]2C4H10O, features a dinuclear chloride-bridged palladium complex bearing two equivalents of the novel monoanionic mixed valent (3-P)—N—(5-P) ligand. A metal catalyzed coupling of two aminoiminophosphines and a shift of one chlorine from the metal to the phosphorus results in the (3-P)—N—(5-P) ligand. The molecule contains a planar bimetallic Pd2Cl2 core with a crystallographic centre of inversion at the mid-point of the Pd Pd line. The Pd atoms are in a distorted square-planar arrangement, where the P/Pd/P and Cl/Pd/Cl planes are twisted with respect to each other by a dihedral angle of 7.57 (4) . The P—Pd—P bite angle is 71.380 (18) . Intramolecular C—H Cl interactions are observed. In the crystal, the diethyl ether solvent molecule is disordered over two sites, with an occupancy ratio of 0.788 (5):0.212 (5).
Structure description Low-valent phosphorous compounds, such as aminoiminophosphines R2N—P NR, are versatile ligands. Due to their unsaturated P N double bond they can undergo [2 + 2] cycloaddition to yield the cyclodiphosphadiazanes (Niecke et al., 1976). In the presence of dichlorido(1,5-cyclooctadiene)palladium(II), two N—P N molecules undergo a [2 + 1] cycloaddition which results in a kind of azadiphosphiridine or, respectively, a monoanionic six-electron-donor ligand (Scherer & Bru¨ck, 1987). In the course of coordination to dichlorido(1,5-cyclooctadiene)palladium(II), one chlorine is transferred from the metal centre to the PIII atom. As a consequence, two palladium cores dimerize by building a dinuclear chloride-bridged palladium complex with two equivalents of the IUCrData (2016). 1, x160986
http://dx.doi.org/10.1107/S241431461600986X
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data reports Table 1 ˚ , ). Hydrogen-bond geometry (A D—H A i
C3—H3C Cl1 C14—H14C Cl2
D—H
H A
D A
D—H A
0.98 0.98
2.72 2.67
3.564 (3) 3.585 (2)
144 156
Symmetry code: (i) x þ 1; y þ 1; z þ 1.
monoanionic mixed-valent (3-P)—N—(5-P) ligand. The molecule contains a planar bimetallic Pd2Cl2 core with a crystallographic centre of inversion at the mid-point of Pd Pd line (Fig. 1). The Pd—Cl bond lengths are 2.4296 (5) ˚ , which are similar to other dinuclear and 2.4815 (4) A chloride-bridged palladium(II) complexes (average Pd—Cl = ˚ for Pd—Cl—Pd > 85 ; Orpen et al., 1989). Due to the 2.432 A ˚ there is no metal–metal large Pd Pd distance of 3.521 A interaction. The Pd atoms are in a distorted square-planar arrangement where the P1/Pd1/P2 and Cl1/Pd1/Cl1i planes [symmetry code: (i) x + 1, y + 1, z + 1] are twisted with respect to each other by an angle of 7.57 (4) . The mixed valent (3-P)—N—(5-P) ligand is remarkable, with the ability to form a four-membered metallacycle that is nearly planar, with a P2—N2—P1—Pd1 torsion angle of 6.45 (7) . The different Pd—P distances are 2.1947 (5) (3-P—Pd) and ˚ (5-P—Pd). Compared to a 3-P–metal bond, the 2.2294 (5) A Table 2 Experimental details. Crystal data Chemical formula
[Pd2(C18H54Cl2N4P2Si6)2Cl2]2C4H10O 1617.10 Triclinic, P1 150 12.7331 (3), 12.9694 (3), 14.6354 (3) 104.1592 (6), 101.3576 (6), 112.6871 (6) 2044.32 (8) 1 Mo K 0.86 0.42 0.40 0.18
Mr Crystal system, space group Temperature (K) ˚) a, b, c (A , , ( ) ˚ 3) V (A Z Radiation type (mm1) Crystal size (mm) Data collection Diffractometer Absorption correction Tmin, Tmax No. of measured, independent and observed [I > 2(I)] reflections Rint ˚ 1) (sin /)max (A Refinement R[F 2 > 2(F 2)], wR(F 2), S No. of reflections No. of parameters No. of restraints H-atom treatment ˚ 3) max, min (e A
Bruker APEXII CCD Multi-scan (SADABS; Bruker, 2014) 0.77, 0.86 40794, 9871, 8984 0.021 0.661
0.029, 0.076, 1.04 9871 367 29 H-atom parameters constrained 0.95, 0.92
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), XP in SHELXTL (Sheldrick, 2008), and publCIF (Westrip, 2010).
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[Pd2(C18H54Cl2N4P2Si6)2Cl2]2C4H10O
Figure 1 The molecular structure of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 30% probability level. H atoms and disordered solvent have been omitted for clarity. [Symmetry code: (i) x + 1, y + 1, z + 1.]
5-P–metal bond length is elongated. A longer 5-P–metal bond compared to the 3-P–metal bond length was also observed in a Pd complex bearing a mixed-valent (3-P)—N— (5-P) ligand (du Mont et al., 2009) The P1—Pd1—P2 bite angle is 71.380 (18) . For the 5 ˚ ( -P) N double bond (N3—P2), a value of 1.5346 (17) A was observed. All other P—N bond distances range from ˚ (P2—N2). Compared 1.6519 (16) (P1—N1) to 1.7772 (16) A ˚ ; Pyykko¨, to the calculated P—N single-bond distance (1.82 A 2015) they are obviously shorter and display some multiple bonding character. The calculated P N double bond length is ˚ (Pyykko¨, 2015). This might be explained by being a 1.62 A consequence of hyperconjugation in the alternating P—N ligand backbone. Similar but mononuclear iron and platinum complexes with mixed-valent (3-P)—N—(5-P) ligands have been reported (du Mont et al., 2009; Jones et al., 2015). Intramolecular C—H Cl interactions are observed (Table 1). The crystal of the title compound contains a diethyl ether solvent molecule which is disordered over two sites with an occupancy ratio of 0.788 (5):0.212 (5).
Synthesis and crystallization A pale-yellow solution of 1.27 mmol of the aminoiminophosphine (TMS)2N—P N(TMS) in 5 ml toluene was added dropwise to a bright-yellow suspension of 0.58 mmol dichlorido(1,5-cyclooctadiene)palladium(II) in 15 ml toluene. After stirring for 10 min at room temperature, the yellow solution became clear. It was stirred for another 12 h before the solvent was reduced in a vacuum. The resulting yellow solution was filtered. After adding diethyl ether, it was cooled to 233 K to obtain yellow crystals of the title compound that were suitable for X-ray analysis (yield 77%; m.p. decomposition above 347 K). Analysis calculated for C36H108Cl4N8P4Pd2Si12: C 29.44, H 7.41, N 7.63, P 8.43%; found: C 29.24, H IUCrData (2016). 1, x160986
data reports 7.66, N 7.07, P 8.51%. 1H NMR (400 MHz, C6D6): 0.44 (s, 24H, 2 TMS), 0.57 (s, 24H, 2 TMS), 0.69 (s, 12H, TMS), 0.74 (s, 12H, TMS). 13C (100.6 MHz, C6D6): 3.8 (TMS), 5.7 (TMS), 6.3 (TMS), 7.5 (TMS). 31P (121 MHz, C6D6): 88.52 (s), 28.06 (br, s). 29Si (79.5 MHz, C6D6): 8.32 (2 N-TMS), 11.34 (4 N-TMS). MS CI (m/z) 1466 [M + 2]+, 1275 [C30H90N7P3Pd2Si10]+, 1158 [C27H81N6P3Pd2Si9 + 3H]+. IR ATR (cm1) 2896.9 (w), 2957.2 (w).
Refinement Crystal data, data collection and structure refinement details are summarized in Table 2. The diethyl ether molecule is disordered over two sites with refined occupancies 0.788 (5):0.212 (5). DFIX and DANG instructions were used to improve the geometry of the disordered solvent molecule. Additionally, the anisotropic displacement parameters of O1A and O1B were restrained to be equal (SIMU). Atoms C19A, C19B C20A, C20B, C21A, C21B, C22A and C22B were refined isotropically. A SIMU instruction was also applied for these atoms.
IUCrData (2016). 1, x160986
Acknowledgements The publication of this article was funded by the Open Access Fund of the Leibniz Association.
References Bruker (2013). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Bruker (2014). APEX2 and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Jones, P. G., Daniliuc, C., du Mont, W.-W. & Goers, C. (2015). Private communication (refcode BUCGIR). CCDC, Cambridge, England. Mont, W.-W. du, Lungu, D., Daniliuc, C., Jones, P. G., Nyulaszi, L., Benko, Z. & Bartsch, R. (2009). Eur. J. Inorg. Chem. pp. 2901–2905. Niecke, E., Flick, W. & Pohl, S. (1976). Angew. Chem. 88, 305–306. Orpen, A. G., Brammer, L., Allen, F. H., Kennard, O., Watson, D. G. & Taylor, R. (1989). J. Chem. Soc. Dalton Trans. pp. S1–S83. Pyykko¨, P. (2015). J. Phys. Chem. A, 119, 2326–2337. Scherer, O. J. & Bru¨ck, T. (1987). Angew. Chem. 99, 59–61. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
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[Pd2(C18H54Cl2N4P2Si6)2Cl2]2C4H10O
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full crystallographic data IUCrData (2016). 1, x160986
[doi:10.1107/S241431461600986X]
Di-µ-chlorido-bis({4-[bis(trimethylsilyl)amino]-6-chloro-2,2,8,8-tetramethyl-5,7bis(trimethylsilyl)-3,5,7-triaza-4,6-diphospha-2,8-disilanon-3-en-4-idoκ2P,P′}palladium(II)) diethyl ether disolvate Martha Höhne, Bernd H. Müller, Anke Spannenberg and Uwe Rosenthal Di-µ-chlorido-bis({4-[bis(trimethylsilyl)amino]-6-chloro-2,2,8,8-tetramethyl- 5,7-bis(trimethylsilyl)-3,5,7triaza-4,6-diphospha-2,8-disilanon-3-en-4-ido-κ2P,P′}palladium(II)) diethyl ether disolvate Crystal data [Pd2(C18H54Cl2N4P2Si6)2Cl2]·2C4H10O Mr = 1617.10 Triclinic, P1 a = 12.7331 (3) Å b = 12.9694 (3) Å c = 14.6354 (3) Å α = 104.1592 (6)° β = 101.3576 (6)° γ = 112.6871 (6)° V = 2044.32 (8) Å3
Z=1 F(000) = 852 Dx = 1.314 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 9897 reflections θ = 2.5–29.0° µ = 0.86 mm−1 T = 150 K Prism, yellow 0.42 × 0.40 × 0.18 mm
Data collection Bruker APEXII CCD diffractometer Radiation source: fine-focus sealed tube Detector resolution: 8.3333 pixels mm-1 φ and ω scans Absorption correction: multi-scan (SADABS; Bruker, 2014) Tmin = 0.77, Tmax = 0.86
40794 measured reflections 9871 independent reflections 8984 reflections with I > 2σ(I) Rint = 0.021 θmax = 28.0°, θmin = 1.5° h = −16→16 k = −17→17 l = −19→19
Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.029 wR(F2) = 0.076 S = 1.04 9871 reflections 367 parameters 29 restraints
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Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ2(Fo2) + (0.0355P)2 + 2.0017P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.001 Δρmax = 0.95 e Å−3 Δρmin = −0.92 e Å−3
data-1
data reports Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
C1 H1A H1B H1C C2 H2A H2B H2C C3 H3A H3B H3C C4 H4A H4B H4C C5 H5A H5B H5C C6 H6A H6B H6C C7 H7A H7B H7C C8 H8A H8B H8C C9 H9A H9B H9C C10 H10A H10B
x
y
z
Uiso*/Ueq
0.6444 (3) 0.6442 0.7235 0.5825 0.6250 (3) 0.5583 0.7017 0.6217 0.7322 (2) 0.7625 0.7983 0.6988 0.1995 (2) 0.1965 0.1485 0.1705 0.3946 (2) 0.4650 0.3262 0.4128 0.3559 (3) 0.3386 0.2941 0.4351 0.0637 (2) 0.0499 0.0159 0.0397 0.2971 (3) 0.3813 0.2536 0.2936 0.2465 (2) 0.2120 0.2056 0.3325 −0.0606 (2) −0.1082 −0.1109
0.1775 (4) 0.1971 0.1847 0.0954 0.2550 (3) 0.1781 0.2535 0.3190 0.4325 (3) 0.4829 0.4239 0.4697 0.0972 (2) 0.1676 0.0265 0.0858 0.1077 (2) 0.0928 0.0417 0.1826 −0.0021 (3) 0.0099 −0.0795 −0.0006 0.2099 (2) 0.1267 0.2226 0.2270 0.2308 (3) 0.2862 0.1990 0.1648 0.4447 (2) 0.4890 0.4191 0.4963 0.1388 (2) 0.1654 0.0892
0.2536 (4) 0.3226 0.2523 0.2142 0.0734 (2) 0.0276 0.0751 0.0506 0.2872 (2) 0.2489 0.3262 0.3323 0.1565 (2) 0.1972 0.1687 0.0859 0.3154 (2) 0.3264 0.3191 0.3666 0.0910 (2) 0.0272 0.0855 0.1080 −0.0030 (2) −0.0250 −0.0564 0.0564 −0.04103 (17) −0.0280 −0.1127 −0.0183 −0.00733 (17) 0.0302 −0.0789 0.0085 0.2237 (2) 0.1831 0.2544
0.0864 (14) 0.130* 0.130* 0.130* 0.0517 (7) 0.078* 0.078* 0.078* 0.0539 (7) 0.081* 0.081* 0.081* 0.0443 (6) 0.066* 0.066* 0.066* 0.0433 (6) 0.065* 0.065* 0.065* 0.0583 (8) 0.087* 0.087* 0.087* 0.0447 (6) 0.067* 0.067* 0.067* 0.0472 (7) 0.071* 0.071* 0.071* 0.0392 (5) 0.059* 0.059* 0.059* 0.0481 (6) 0.072* 0.072*
IUCrData (2016). 1, x160986
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