The first ruthenium complex of a heteroleptic organostannylene: [4-tbu-2, 6-{p(o)(o-ipr)2}2c6h2]sn(cl) ru(c6h6)cl2

Article abstract of DOI:10.1002/zaac.200900045

The synthesis of the intramolecularly coordinated organostannylene ruthenium complex [4-tBu-2, 6-{P(O)(O-iPr)₂}₂C ₆H₂]Sn(Cl)Ru(C₆H₆)Cl₂, 1, is reported. It is characterized by el

Full text of DOI:10.1002/zaac.200900045

ARTICLE
DOI: 10.1002/zaac.200900045
The First Ruthenium Complex of a Heteroleptic Organostannylene:
[4-tBu-2,6-{P(O)(O-iPr)2}2C6H2]Sn(Cl)Ru(C6H6)Cl2
[a]
[a]
[a]
´
Vajk Deaky, Markus Schürmann, and Klaus Jurkschat*
Keywords: Tin; Ruthenium; Heteroleptic organostannylene; Molecular structure
Abstract. The synthesis of the intramolecularly coordinated
organostannylene ruthenium complex [4-tBu-2,6-{P(O)(O-iPr)2}2-
C6H2]Sn(Cl)Ru(C6H6)Cl2, 1, is reported. It is characterized by
analysis. In compound 1·C7H8 the tin atom is five-coordinate and
shows a strongly distorted trigonal-bipyramidal configuration. The
˚
intramolecular OϪSn distances are 2.291(3) and 2.394(3) A. The
1
elemental analysis, H, 13C, 31P, 119Sn NMR spectroscopy, and, as
SnϪRu distance is 2.5856 A.
˚
its toluene solvate 1·C7H8, by single-crystal X-ray diffraction
ported so far and nothing is known on the reactivity of the
latter towards heteroleptic organostannylenes, RSnX (X ϭ
electronegative substituent such as halide, alkoxide etc.).
Recently, we and others have shown that intramolecularly
coordinated heteroleptic organostannylenes RSnCl (R ϭ [4-
tBu-2,6-{P(O)(OiPr}2C6H2], 2,6-(Me2NCH2)2C6H3) react
with palladium(II) chloride, PdCl2, or its bis(triphenylphos-
phane) complex PdCl2(PPh3)2 as two-electron donors to
give the corresponding complexes [Pd(Cl2)(SnRCl)2], rather
than under insertion into the PdϪCl bond [18, 19]. In con-
tinuation of our systematic studies concerning the reactivity
of such heteroleptic organostannylenes towards transition
metal compounds we report here the synthesis and struc-
ture of the title complex.
Introduction
The first tin-ruthenium heterobimetallic compound was
reported in 1967 [1]. A number of tin-ruthenium species
have been published since then [2Ϫ17] and representative
examples A Ϫ F are depicted in Scheme 1. When divalent
tin compounds are employed for the formation of tin-ru-
thenium bonds, different reaction paths are observed. Thus,
tin(II) chloride, SnCl2, reacts with RuϪCl and RuϪRu
bonds under insertion to give the corresponding trichloro-
stannate and SnCl2-bridged complexes, respectively [3, 10],
whereas reaction with the hexanuclear ruthenium cluster
[Ru6C(CO)17] provided, with substitution of carbon mon-
oxide, the corresponding dichlorostannylene complex
[Ru6C(CO)16SnCl2] [8]. Diorganostannylenes SnR2 (R ϭ
CH(SiMe3)2, 2,4,6-iPr3C6H2) react with Ru3(CO)12 exclus-
ively as two-electron donors and form heterobimetallic clus-
ters such as compound F (Scheme 1) and [Ru3(CO)9(µ-
SnR2)3] in which the tin atoms bridge two ruthenium atoms
Results and Discussion
The reaction of the intramolecularly coordinated hetero-
[4, 6]. To the best of our knowledge, no reaction of dior- leptic organostannylene [4-tBu-2,6-{P(O)(OiPr}2C6H2]SnCl
ganostannylenes, SnR2, with RuϪCl bond has been re- with the benzenedichlororuthenium dimer, [Ru(C6H6)Cl2]2,
gave the corresponding organostannylene ruthenium com-
plex [4-tBu-2,6-{P(O)(O-iPr)2}2C6H2]Sn(Cl)Ru(C6H6)Cl2
(1) in good yield [Equation (1)]. Recrystallization from tolu-
* Prof. Dr. K. Jurkschat
ene provided red air-stable single crystals of the toluene
solvate, 1·C7H8. The latter is well soluble in common
organic solvents such as dichloromethane, tetrahydro-
furane, and toluene.
Fax: ϩ49-231-5048
E-Mail: klaus.jurkschat@uni-dortmund.de
[a] Lehrstuhl für Anorganische Chemie II
Technische Universität Dortmund
44221 Dortmund, Germany
1380
 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2009, 635, 1380Ϫ1383

The first Ruthenium Complex of a Heteroleptic Organostannylene
Scheme 1.
The molecular structure of compound 1·C7H8 is shown
The tin atom is pentacoordinate and exhibits a strongly
in Figure 1 and selected bond lengths and bond angles are distorted trigonal-bipyramidal configuration with C(1),
summarized in Table 1.
Cl(1), and Ru(1) occupying the equatorial and O(1) and
O(2) occupying the axial positions; with the major
deviations from the ideal angles being found for
C(1)ϪSn(1)ϪRu(1)
140.99(12)°,
C(1)ϪSn(1)ϪCl(1)
96.04(12)°, and O(1)ϪSn(1)ϪO(2) 155.43(9)°. The intra-
molecular O(1)ϪSn(1) and O(2)ϪSn(1) distances are non-
˚
equivalent and amount to 2.291(3) and 2.394(3) A, respec-
tively. These distances are shorter than those observed
for the parent organotin(II) chloride [4-tBu-2,6-
˚
{P(O)(OiPr)2}2C6H2]SnCl [2.430(2), 2.427(2) A] [20] and
indicate the electron-withdrawing capacity of the
Ru(C6H6)Cl2 moiety making the tin atom in compound 1
more Lewis-acidic. In the related complexes [4-tBu-2,6-
{P(O)(OiPr)2}2C6H2](Cl)SnM(CO)5 (M ϭ Cr [20], Mo [21],
W [22]) these distances fall into the narrow range between
˚
2.313(2) (M ϭW] and 2.347(2) A (M ϭ Cr].
˚
The SnϪRu distance of 2.5856(6) A is at the rather short
end of the range among the crystallographically established
˚
such bonds; the shortest being 2.543(1) A found for
Ru(C6H6)(SnCl3)(CH3)[Ph2PNHCH(CH3)Ph] [3] and the
˚
longest being 3.140(2) A found for [Ru6C(CO)16-
(SnCl3)]Ϫ[8].
The identity of compound 1 is preserved in solution
(C6D6) as it is especially evidenced by the strong low-
frequency 119Sn (δ ϭ Ϫ387) and 31P (δ ϭ 27.7) NMR
chemical shifts as well as the J(119SnϪ31P) coupling of
242 Hz. For the organotin(II) chloride [4-tBu-2,6-
{P(O)(OiPr)2}2C6H2]SnCl these values are δ119Sn ϭ Ϫ99,
δ31P ϭ 37.8 and J(119SnϪ31P) 119 Hz [20]. The methyl pro-
tons of the isopropyl substituents show four equally intense
Figure 1. ORTEP-drawing of a molecule of 1. The toluene solvate
molecule is omitted for clarity.
˚
Table 1. Selected bond lengths /A and bond angles /° of 1·C7H8.
Sn(1)ϪO(1)
Sn(1)ϪO(2)
Sn(1)ϪC(1)
Sn(1)ϪCl(1)
Sn(1)ϪRu(1)
2.291(3)
2.394(3)
2.158(4)
C(1)ϪSn(1)ϪCl(1)
C(1)ϪSn(1)ϪRu(1)
Cl(1)ϪSn(1)ϪRu(1)
96.04(12)
140.99(12)
121.81(3)
76.12(3)
1
doublet resonances in the H NMR spectrum indicating (i)
2.4283(13) Sn(1)ϪRu(1)ϪCl(11)
2.5856(6) Sn(1)ϪRu(1)ϪCl(12)
90.57(3)
hindered rotation about the OϪC bond and (ii) the tin
atom in compound 1 to be configurationally stable on the
NMR time scale.
Ru(1)ϪCl(11) 2.4288(13) Cl(12)ϪRu(1)ϪCl(11) 86.57(5)
Ru(1)ϪCl(12) 2.4088(13) O(1)ϪSn(1)ϪO(2) 155.43(9)
Z. Anorg. Allg. Chem. 2009, 1380Ϫ1383
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www.zaac.wiley-vch.de
1381

´
V. D e a ky, M. Schürmann, K. Jurkschat
ARTICLE
The electrospray ionisation mass spectrum in the positive Table 2. Cystal data and structure refinement of 1·C7H8.
mode of compounds 1 showed a high-intense (100 %) mass
Empirical formula
Formula weight
C28H45Cl3O6P2RuSn·C7H8
857.82
173(1)
0.71073
triclinic
¯
P1
cluster centred at m/z 581.2 that is assigned to the organo-
stannylene cation [4-tBu-2,6-{P(O)(OiPr)2}2C6H2]Snϩ. Temperature /K
˚
Wavelength /A
There was also a rather low-intense (approximately 3 %)
Crystal system
mass cluster centred at 830.1 that is assigned to [4-tBu-2,6-
Space group
{P(O)(OiPr)2}2C6H2]SnRuCl2(C6H6)ϩ.
Unit cell dimensions
˚
a /A
9.866(2)
12.895(2)
17.416(3)
75.929(8)
87.591(7)
84.334(7)
2138.3(6)
2
˚
b /A
˚
c /A
Experimental Section
Ͱ /°
β /°
General. All solvents were dried and purified by standard pro-
γ /°
cedures. All reactions were carried out in an atmosphere of dry
argon. Bruker DPX-300 and DRX-400 spectrometers were used to
3
˚
Volume /A
Z
obtain 1H, 31P, and 119Sn NMR spectra at ambient temperature.
1H, 31P, and 119Sn NMR chemical shifts are given in ppm and were
referenced to Me4Si, H3PO4 (85 %, 31P) and Me4Sn (119Sn). El-
emental analyses were performed on a LECO-CHNS-932 analyzer.
Dc /g·cmϪ3
1.486
1.238
972
Absorption coefficient /mmϪ1
F(000)
Crystal size, mm
0.10 ϫ 0.08 ϫ 0.06
2.98 to 27.48
35070
9786 [R(int) ϭ 0.052]
Full-matrix least-squares on F2
9786 / 0 / 442
0.673
R1 ϭ 0.036, wR2 ϭ 0.064
R1 ϭ 0.127, wR2 ϭ 0.070
θrange for data collections /°
Reflections collected
Independent reflections
Refinement method
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I>2σ (I)]
R indices (all data)
The electrospray mass spectrum was recorded with a Thermoquest-
Finnigan instrument using CH3CN as the mobile phase. The
samples were introduced as solution in CH3CN via a syringe pump
operating at 0.5 µL·minϪ1. The capillary voltage was 4.5 kV,
whereas the cone skimmer voltage varied between 50 and 250 kV.
Identification of the expected ions was assisted by comparison of
experimental and calculated isotope distribution patterns. The m/z
values reported correspond to those of the most intense peak in
the corresponding isotope pattern.
Largest diff. peak and hole /e·AϪ3 1.462 and Ϫ0.716
12 Union Road, Cambridge, CB2 1EZ, UK (Fax: ϩ44-1223-
336033; E-Mail: deposit@ccdc.cam.ac.uk).
X-ray Crystallography
Synthesis of ({4-tBu-2,6-[P(O)(O-iPr)2]2C6H2}SnCl)-
Ru(C6H6)Cl2 ·C7H8
Intensity data for the red crystal of ({4-tBu-2,6-[P(O)(O-
iPr)2]2C6H2}SnCl)Ru(C6H6)Cl2 ·C7H8 was collected on a Nonius
KappaCCD diffractometer with graphite-monochromated Mo-Kα
radiation at 173 K. The data collection covered almost the whole
sphere of reciprocal space with 4 sets at different κ-angles and 257
frames via ω-rotation (∆/ω ϭ 2°) at two times 15s per frame. The
crystal-to-detector distance was 3.4 cm. Crystal decay was moni-
tored by repeating the initial frames at the end of data collection.
Analyzing the duplicate reflections there was no indication for any
decay. The structure was solved by direct methods SHELXS97 [23]
and successive difference Fourier syntheses. Refinement applied
full-matrix least-squares methods SHELXL97 [24]. The hydrogen
atoms were placed in geometrically calculated positions using a rid-
ing model with Uiso constrained at 1.2 for non-methyl groups and
1.5 for methyl groups times Ueq of the carrier atom. The oxygen
atoms O1, O1Ј, O1Љ, O2, O2Ј, O2Љ are not disordered. The solvent
molecule toluene and one isopropyl group are disordered over two
positions with occupancies of 0.35 (C(34Ј), C(35Ј), C(36Ј)) of 0.5
(C(41) > C(47), C(51) > C(57)) and of 0.65 (C(34), C(35), C(36Ј)).
The carbon atoms of the solvent molecule toluene (C(41) > C(47),
C(51) > C(57)) were refined isotropically. Atomic scattering factors
for neutral atoms and real and imaginary dispersion terms were
taken from International Tables for X-ray Crystallography [25]. The
figures were created by SHELXTL [26]. Crystallographic data are
given in Table 2.
{4-tBu-2,6-[P(O)(O-iPr)2]2C6H2}SnCl (1.0 g, 1.62 mmol) was ad-
ded to a suspension of Ru2(C6H6)2Cl4 (0.40 g, 0.81 mmol) in
toluene (5 mL). After the reaction mixture had been stirred for 12 h
the solution was filtered and the toluene was removed in vacuo to
give
a solid residue. Recrystallization of this residue from
toluene/n-hexane gave 0.87 g, (56 %) of {4-tBu-2,6-[P(O)(O-
iPr)2]2C6H2}Sn(Cl)Ru(C6H6)Cl2 as red crystals of m.p. 182 °C
(decomposition), suitable for X-ray diffraction analysis.
C35H53Cl3O6P2RuSn, 865.74 g/mol: C, 43.89; H, 5.58. Found: C,
43.7; H, 5.4 %.
1H NMR (300.13 MHz, C6D6): δ ϭ 0.97 (d, 6 H, CH(CH3)2,
3J(1HϪ1H) ϭ 6.1 Hz), 1.07 (s, 9 H, C(CH3)3, 1.10 (d, 6 H,
CH(CH3)2, J(1HϪ1H)
ϭ 6.1 Hz), 1.31 (d, 6 H, CH(CH3)2,
J(1HϪ1H) ϭ 6.0 Hz), 1.43 (d, 6 H, CH(CH3)2, J(1HϪ1H) ϭ
6.0 Hz), 2.17 (s, 3 H, C6H5-CH3), 4.91 (m, 4 H, CH(CH3)2,
3
3J(1HϪ1H) ϭ 6.1, J(31PϪ1H) ϭ 7.5 Hz), 5.47 (m, 8 H, CH(CH3)2
ϩ η6-C6H6), 8.02 (d, 4 H, CHaryl, J(31PϪ1H) ϭ 13.8 Hz). 31P{1H}
3
NMR (121.49 MHz, C6D6 δ ϭ 27.7 (J(31PϪ117/119Sn) ϭ 232/
243 Hz). 119Sn{1H} NMR (111.92 MHz, C6D6): δ ϭ Ϫ387 (t,
J(119SnϪ31P) ϭ 242 Hz. Electrospray MS: m/z 581.2, 530.0.
References
Crystallographic data for the structure reported in this paper have
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as supplementary material publication no. CCDC-716352. Copies
of the data can be obtained free of charge on application to CCDC,
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The first Ruthenium Complex of a Heteroleptic Organostannylene
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Received: January 16, 2009
Published Online: April 8, 2009
Z. Anorg. Allg. Chem. 2009, 1380Ϫ1383
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www.zaac.wiley-vch.de
1383