Syntheses and crystal structures of ruthenium complexes with bidentate salicylaldiminato and dithiophosphato ligands

Article abstract of DOI:10.1515/znb-2018-0045

Treatment of the bidentate Schiff base 2-[(2,6-diisopropyl-phenylimino)-methyl]-phenol (HL1) with one equivalent of (Et₄N)[RuCl₄(MeCN)₂] in the presence of triethylamine afforded (Et₄N)[RuCl₃(κ^2<

Full text of DOI:10.1515/znb-2018-0045

Z. Naturforsch. 2018; 73(5)b: 329–335
Li-Hua Tang, Fule Wu, Hui Lin, Ai-Quan Jia and Qian-Feng Zhang*
Syntheses and crystal structures of ruthenium
complexes with bidentate salicylaldiminato
and dithiophosphato ligands
https://doi.org/10.1515/znb-2018-0045
Schiff base complexes bearing a sulfonamide moiety are
efficient catalysts in the transfer hydrogenation of aceto-
phenone derivatives with the turnover frequency reaching
1260 h−1 [3]. Schiff base functionalized second-generation
Grubbs catalysts exhibit greater stability and activity for
the ring opening metathesis polymerization than their
parent first-generation Schiff base catalysts by adjusting
different substituents [5]. On the other hand, there has
been increasing interest in ruthenium thiolate complexes
in the past decades, partly due to the high catalytic activ-
ity of RuS2 in various hydrogenation processes [6]. Many
structurally diverse and catalytically active ruthenium thi-
olate complexes have been reported to date [7, 8]; however,
the ruthenium complexes with dithio ligands, such as
dithiocarbamate, dithiocarbonate, dithiophosphate, and
dithiophosphonate, are relatively rare [9–11]. Dialkyl-
dithiophosphates (RO)2PS2− (R=Me, Et, iPr) are typical and
versatile 1,1′-dithio ligands that have been widely used
in the synthesis of various transition metal complexes. A
few ruthenium(II) complexes with one and two dialkyl-
Received February 19, 2018; accepted March 30, 2018
Abstract: Treatment of the bidentate Schiff base
2-[(2,6-diisopropyl-phenylimino)-methyl]-phenol
(HL1)
with one equivalent of (Et4N)[RuCl4(MeCN)2] in the pres-
ence of triethylamine afforded (Et4N)[RuCl3(κ2-N,O-L1)-
(MeCN)] (1), which reacted with two equivalents of
K[S2P(OiPr)2] to produce a neutral ruthenium(III) complex
[Ru(κ2-N,O-L1){η2-S2P(OiPr)2}2] (2) bearing both salicyla-
ldiminato and dithiophosphato ligands. Reactions of the
bidentate Schiff bases 2-[(3-chloro-phenylimino)-methyl]-
phenol (HL2) and 2-[(2,4,6-trimethyl-phenylimino)-
methyl]-phenol (HL3) with one equivalent of [Ru(CO)2Cl2]
in the presence of triethylamine led to formation of the
corresponding anionic ruthenium(II) carbonyl complexes
(Et3NH)[RuCl2(κ2-N,O-L2)(CO)2] (3) and (Et3NH)[RuCl2(κ2-
N,O-L3)(CO)2] (4). The molecular structures of com-
plexes 2–4 have been determined by single-crystal X-ray
diffraction.
Keywords: crystal structure; dithiophosphate; ruthenium; dithiophosphate ligands [12, 13] and ruthenium(III) com-
salicylaldimine; synthesis.
plexes with three dialkyldithiophosphate ligands have
been reported [14]. Previously, we investigated the coor-
dination modes and reactivity of several N,O-bidentate,
N,O,S-tridentate, and N2,O2-tetradentate Schiff bases
toward ruthenium(II)/(III) metal centers [15–18], as well
as ruthenium complexes with dithiodiethylphosphate
ligands [12]. The present article reports the syntheses of
three ruthenium complexes with different bidentate Schiff
base ligands and one ruthenium(III) complex with both
salicylaldiminato and dithiophosphato ligands and their
characterization by spectral data and single-crystal X-ray
diffraction.
1 Introduction
Schiff base compounds obtained from the condensation
reaction of different substituted salicylaldehydes and
primary amines have been widely used in coordination
chemistry with transition metals. Typically, ruthenium
complexes with bidentate Schiff base ligands have been
found to exhibit impressive stability and activity, and
their readily accessible imine ligands allow for catalyst
tuning [1–4]. For example, arene-ruthenium(II)-bidentate
2 Experimental
*Corresponding author: Qian-Feng Zhang, Institute of Molecular
Engineering and Applied Chemistry, Anhui University of Technology,
Ma’anshan, Anhui 243002, P.R. China, Fax +86-555-2312041,
E-mail: zhangqf@ahut.edu.cn
Li-Hua Tang, Fule Wu, Hui Lin and Ai-Quan Jia: Institute of Molecular
Engineering and Applied Chemistry, Anhui University of Technology,
Ma’anshan, Anhui 243002, P.R. China
2.1 General considerations
All synthetic manipulations were carried out under
dry nitrogen by standard Schlenk techniques.
Salicylaldehyde, 2,6-diisopropylaniline, 3-chloroaniline,
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2,4,6-trimethylaniline, and triethylamine were purchased then stirred overnight at room temperature, leading to a
from Alfa Aesar Ltd. and used without further purifica- color change from brown to dark green. After removal of
tion. (Et4N)[RuCl4(MeCN)2] and [Ru(CO)2Cl2] were prepared solvents in vacuo, the residue was extracted with CH2Cl2
according to the methods in the literature [19, 20]. The (2ꢀ×ꢀ5 mL) and the solution was filtered. The filtrate was
Schiff base ligands HL1, HL2, and HL3 were prepared by layered with hexane (20 mL) at room temperature, and
refluxing a methanolic solution of the salicylaldehyde dark green block-shaped crystals of [Ru(κ2-N,O-L1)-
and substituted anilines in an equal molar ratio [21]. {S2P(OiPr)2}2] (2) were obtained after 5 days. Yield: 76 mg,
K[S2P(OiPr)2] was synthesized from the reaction of P4S10, 63% (based on Ru). – μeffꢀ=ꢀ1.97 μB. – IR (KBr disc, cm−1):
iPrOH and KOH [22]. NMR spectra were recorded on a 1639 (νC=N), 1241 (νC−O), 1046 (νP−O), 695 and 714 (νP−S). – MS
+
+
Bruker ALX 400 Plus spectrometer operating at 400 MHz (FAB): m/zꢀ=ꢀ707 [M ], 527 [Ru{S2P(OiPr)2}2] , 494 [Ru(L1)-
for H. Chemical shifts (δ, ppm) were reported with refer- {S2P(OiPr)2}] , 314 [Ru{S2P(OiPr)2}] , 281 [Ru(L1)] . – Anal.
ence to SiMe4 (1H). Infrared spectra (KBr) were recorded calcd. for C31H50NO5P2S4Ru: C 52.67, H 7.13, N 1.98; found
on a Perkin-Elmer 16 PC FT-IR spectrophotometer with C 52.62, H 7.20, N 2.03%.
use of pressed KBr pellets and positive FAB mass spectra
1
+
+
+
were recorded on a Finnigan TSQ 7000 spectrometer. The
2.4 Synthesis of triethylammonium
magnetic moment for the solid sample was measured by
ruthenium(II) bicarbonyl dichloride κ2-
a Sherwood magnetic susceptibility balance at room tem-
N,O-2-[(3-chloro-phenylimino)-methyl]-
perature. Elemental analyses were carried out using a
phenolate (Et3NH)[RuCl2(κ2-N,O-L2)(CO)2] (3)
Perkin-Elmer 2400 CHN analyzer.
To a slurry of [Ru(CO)2Cl2] (57 mg, 0.25 mmol) in DMF
2.2 Synthesis of tetraethylammonium
(5 mL) was added a solution of HL2 (58 mg, 0.25 mmol) and
ruthenium(III) acetonitrile κ2-N,O-2-
Et3N (56 mg, 0.50 mmol) in EtOH (5 mL). The mixture was
[(2,6-diisopropyl-phenylimino)-
methyl]-phenolate trichloride
(Et4N)[RuCl3(κ2-N,O-L1)(MeCN)] (1)
heated at 90°C with stirring overnight leading to a color
change from yellow to orange. Addition of Et2O (30 mL)
to the reaction solution gave an orange precipitate that
was filtered and washed with Et2O and hexane. The mate-
To a solution of (Et4N)[RuCl4(MeCN)2] (114 mg, 0.25 mmol) rial was dissolved in CH2Cl2 (10 mL) and filtered, and the
in DMF (10 mL) was added a solution of HL1 (70 mg, clear orange filtrate was layered with Et2O (20 mL) at room
0.25mmol)andEt3N(28mg, 0.25mmol)inEtOH(5mL), and temperature. Orange block-shaped crystals of [Et3NH]-
then the mixture was stirred overnight at reflux, leading to [RuCl2(κ2-N,O-L2)(CO)2] (3) were harvested after 1 week.
a color change from orange to brown. After the removal of Yield: 97 mg, 69%. – IR (KBr disc, cm−1): 3428 (vN−H), 1976
1
solvents in vacuo, the residue was extracted with CH2Cl2 and 2012 (νC≡O), 1634 (νC=N), 1256 (νC−O); – H NMR (CDCl3,
(2ꢀꢀ×ꢀꢀ5 mL) and the solution was filtered. The filtrate was 400 MHz): δꢀ=ꢀ1.01 (t, 9H, Jꢀ=ꢀ3.0 Hz, CH3), 2.52 (q, 6H,
layered with Et2O (20 mL) at room temperature, and brown Jꢀ=ꢀ3.0 Hz, CH2), 6.73 (d, 1H, Jꢀ=ꢀ4.8 Hz, ArH), 6.85‒6.95 (m,
crystalline product of (Et4N)[RuCl3(κ2-N,O-L1)(MeCN)] (1) 2H, ArH), 7.11 (d, 1H, Jꢀ=ꢀ4.9 Hz, ArH), 7.23 (s, 1H, ArH), 7.38
was isolated after 3 days. Yield: 142 mg, 86% (based on Ru). (d, 2H, Jꢀ=ꢀ5.6 Hz, ArH), 7.56 (d, 1H, Jꢀ=ꢀ6.0 Hz, ArH), 8.39 (s,
+
– μeffꢀ=ꢀ1.99 μB. – IR (KBr disc, cm−1): 2018 (νC≡N), 1635 (νC=N), 1H, –CHꢀ=ꢀN) ppm. – MS (FAB): m/zꢀ=ꢀ457 [RuCl2(L2)(CO)2] ,
+
+
+
+
1232 (νC−O). – MS (FAB): m/zꢀ=ꢀ526 [RuCl3(L1)(MeCN)] , 485 422 [RuCl(L2)(CO)2] , 387 [Ru(L2)(CO)2] , 359 [Ru(L2)(CO)] ,
+
+
+
+
+
[RuCl3(L1)] , 450 [RuCl2(L1)] , 415 [RuCl(L1)] , 380 [Ru(L1)] . 331 [Ru(L2)] . – Anal. calcd. for C21H25N2O3Cl3Ru: C 44.97,
– Anal. calcd. for C29H44N3OCl3Ru: C 52.93, H 6.74, N, 6.38; H 4.49, N 5.00; found C 44.76, H 4.54, N 5.05%.
found C 52.78, H 6.69, N 6.45%.
2.5 Synthesis of triethylammonium
2.3 Synthesis of ruthenium(III) κ2-N,O-2-
ruthenium(II) bicarbonyl dichloride
κ2-N,O-2-[(2,4,6-trimethyl-phenylimino)-
methyl]-phenolate (Et3NH)[RuCl2(κ2-
N,O-L3)(CO)2] (4)
[(2,6-diisopropyl-phenylimino)-methyl]-
phenolate bis-diisopropyldithiophos-
phate [Ru(κ2-N,O-L1){η2-S2P(OiPr)2}2] (2)
A mixture of 1 (99 mg, 0.15 mmol) and K[S2P(OiPr)2] The method was similar to that used for 3, using HL3
(81 mg, 0.32 mmol) was dissolved in THF (20 mL) and (60 mg, 0.25 mmol) instead of HL2. Yield: 88 mg,
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L.-H. Tang et al.: Structures of ruthenium complexes bidentate salicylaldiminato and dithiophosphato ligandsꢂ
ꢂ331
62%. – IR (KBr disc, cm−1): 3431 (vN−H), 1981 and 2027 (νC≡O), on Fꢀ2 using the SHELXTL-2014/7 software package [25, 26].
1630 (νC=N), 1246 (νC−O). – 1H NMR (CDCl3, 400 MHz): δꢀ=ꢀ1.03 All nonhydrogen atoms were refined anisotropically. The
(t, 9H, Jꢀ=ꢀ3.0 Hz, CH3), 2.36 (sꢀꢀ×ꢀꢀ2, 6H + 3H, ArCH3), 2.55 positions of all hydrogen atoms were generated geometri-
(q, 6H, Jꢀ=ꢀ3.0 Hz, CH2), 6.75 (s, 1H, ArH), 6.89 (s, 1H, ArH), cally (Csp3–Hꢀ=ꢀ0.96 and Csp2–Hꢀ=ꢀ0.93 Å) and included in
7.14‒7.25 (m, 2H, ArH), 7.30 (d, 1H, Jꢀ=ꢀ5.6 Hz, ArH), 7.43 the structure factor calculations with assigned isotropic
(d, 1H, Jꢀ=ꢀ5.8 Hz, ArH), 8.45 (s, 1H, –CHꢀ=ꢀN) ppm. – MS thermal parameters but were not refined. EADP, DFIX,
+
+
(FAB): m/zꢀ=ꢀ465 [RuCl2(L3)(CO)2] , 430 [RuCl(L3)(CO)2] , and DELU commands are used in the structure refinement
395 [Ru(L3)(CO)2] , 367 [Ru(L3)(CO)] , 339 [Ru(L3)(CO)2] . of complex 2 due to the disorder of one –OiPr group. The
– Anal. calcd. for C24H32N2O3Cl2Ru: C 50.70, H 5.67, N 4.93; most disagreeing reflections in complex 4 were omitted.
+
+
+
found C 51.03, H 5.62, N 5.01%.
CCDC 1585701 (2), 1585702 (3), and 1585703 (4) contain
the supplementary crystallographic data for this article.
These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre through www.ccdc.
cam.ac.uk/data_request/cif.
2.6 Crystal structure determinations
A summary of crystallographic data and experimental
details for complexes 2, 3, and 4 is given in Table 1. Inten-
sity data were collected on a Bruker SMART APEX 2000 3 Results and discussion
CCD diffractometer using graphite-monochromatized
MoKα radiation (λꢀ=ꢀ0.71073 Å) at Tꢀ=ꢀ296(2) K. The col- As shown in Scheme 1, treatment of (Et4N)[RuCl4(MeCN)2]
lected frames were processed with the software SAINT with one equivalent of the Schiff base 2-[(2,6-diisopro-
[23]. The data was corrected for absorption using the pyl-phenylimino)-methyl]-phenol (HL1) in the presence
program SADABS [24]. The structures were solved by of triethylamine afforded an anionic ruthenium(III)
Direct Methods and refined by full-matrix least-squares complex (Et4N)[RuCl3(κ2-N,O-L1)(MeCN)] (1). One chloro
Table 1:ꢀCrystallographic data and experimental details for [Ru(κ2-N,O-L1){η2-S2P(OiPr)2}2] (2), [Et3NH][RuCl2(κ2-N,O-L2)(CO)2] (3), and [Et3NH]-
[RuCl2(κ2-N,O-L3)(CO)2] (4).
Complex
2
3
4
Empirical formula
C31H50NO5P2S4Ru
807.97
C21H25N2O3Cl3Ru
560.85
Orthorhombic
Pbca
14.285(10)
11.557(8)
29.16(2)
90
C24H32N2O3Cl2Ru
568.49
Orthorhombic
Pbca
11.883(4)
20.344(6)
21.874(6)
90
Formula weight
Crystal system
Space group
a, Å
Triclinic
̅
P1
12.696(4)
12.975(4)
13.893(4)
82.145(6)
75.567(6)
65.794(6)
2019.9(10)
2
b, Å
c, Å
α, deg
β, deg
90
90
90
90
γ, deg
V, Å3
4814(6)
8
5288(3)
8
Z
D
calcd, g cm‒3
1.33
1.55
1.43
Temperature, K
F(000), e
296(2)
296(2)
296(2)
842
2272
2336
μ(MoKα), mm‒1
Refl. total
0.709
1.008
0.821
12075
28082
26351
Refl. unique/Rint
Ref. parameters
R1a/wR2b (Iꢁ>ꢁ2σ(I))
R1a/wR2b (all data)
GoFc
8444/0.0600
397
5487/0.0621
278
5776/0.0306
299
0.0887/0.2283
0.1677/0.2911
1.100
0.0363/0.0787
0.0739/0.0927
1.008
0.0249/0.0614
0.0411/0.0674
1.005
Δρfin (max/min), e Å−3
+1.383/–0.898
+0.333/–0.407
+0.350/–0.463
2
2
2
2
2
aR1ꢁ=ꢁΣꢁ|ꢁ|ꢁFoꢁ|ꢁ–ꢁ|ꢁFcꢁ|ꢁ|ꢁ/Σꢁ|ꢁFoꢁ|; bwR2ꢁ=ꢁ[Σw(Fo –Fc2)2/Σw(Fo )2]1/2, wꢁ=ꢁ[σ2(Fo )ꢁ+ꢁ(AP)2ꢁ+ꢁBP]−1, where Pꢁ=ꢁ(Max(Fo , 0)ꢁ+ꢁ2Fc2)/3; cGoFꢁ=ꢁSꢁ=ꢁ[Σw(Fo –Fc2)2/
(nobs–nparam)]1/2
.
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ꢀL.-H. Tang et al.: Structures of ruthenium complexes bidentate salicylaldiminato and dithiophosphato ligands
−
[Et4N][RuCl4(MeCN)2]
N
[Et4N]+
N
Cl
Et3N, DMF-EtOH, 90 oC
O
Ru
OH
Cl
NCMe
Cl
1
N
S
O
S
Ru
O
P
S
S
O
P
O
O
2
−
Cl
Cl
[Ru(CO)2Cl2]
Et3N, DMF-EtOH, 90 oC
N
[Et3NH]+
N
Cl
O
CO
CO
OH
Ru
Cl
3
[Ru(CO)2Cl2]
Et3N, DMF-THF, 80 oC
N
[Et3NH]+
N
Cl
O
CO
CO
OH
Ru
Cl
4
Scheme 1:ꢀSynthetic reactions of complexes 1–4.
and one acetonitrile ligand in the starting material 1635, 1639, 1634, and 1630 cm−1, respectively. The phenolic
were easily replaced by one bidentate monoanionic L1− O–H absorption of HL1–HL3 was not observed in the IR
ligand. Reaction of complex 1 bearing a labile acetoni- spectra of complexes 1–4, indicating deprotonation and
trile ligand with two equivalents of K[S2P(OiPr)2] in THF coordination of the oxygen atom to the ruthenium center.
gave a neutral ruthenium(III) complex [Ru(κ2-N,O-L1)- The stretching vibration modes of the terminal C≡O groups
{η2-S2P(OiPr)2}2] (2) with both a diisopropyldithiophos- were found at 1976 and 2012 cm−1 for complex 3, and at 1981
phate and a salicylaldimine ligand. It is noted that a and 2027 cm−1 for complex 4. The data compare well with
related complex cis-[Ru(CO)(PEt3){S2P(OEt)2}2] was pre- those of the related ruthenium carbonyl chloride com-
pared by reaction of trans-[RuCl2(CO)2(PEt3)2] with two plexes [Ru(pic)(CO)2Cl2]− (picꢀ=ꢀ2-pyridylcarboxylato, 2047
equivalents of (NH4)[S2P(OiPr)2] in ethanol as a minor and 1973 cm−1) [27] and [Ru(CO)2Cl2(κ2-quinolinedione-
product [10]. Reactions of [Ru(CO)2Cl2] with one equiva- N,O)] (1992–2074 cm−1) [28]. The IR spectrum of complex
lent of 2-[(3-chloro-phenylimino)-methyl]-phenol (HL2) 1 showed the C≡N group of the acetonitrile ligand at
or 2-[(2,4,6-trimethyl-phenylimino)-methyl]-phenol (HL3) 2018 cm−1. The aldimine proton (–CH=N–) resonances of
with the assistance of triethylamine in DMF-EtOH led to the 8.39 ppm for complex 3 and 8.45 ppm for complex 4 appear
formation of the expected anionic ruthenium(II) carbonyl as singlets in the NMR spectra. The positive ion FAB mass
complexes (Et3NH)[RuCl2(κ2-N,O-L2)(CO)2] (3) and (Et3NH)- spectra of 1–4 display the expected peaks corresponding
+
+
+
[RuCl2(κ2-N,O-L3)(CO)2] (4), respectively. The IR spectra of to the molecular ions {[M] , [M–Cl] or [M–Cl–CO] , and
complexes 1–4 showed the band for the CH=N group at [RuL] , or [Ru{S2P(OiPr)2}] } with the characteristic isotopic
+
+
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distribution patterns. The effective magnetic moments for
complexes 1 and 2 are 1.99 and 1.97 μB, respectively, com-
parable with other ruthenium(III) dithiophosphates (low-
spin d5, Sꢀ=ꢀ½) [14].
The structures of complexes 2–4 have been estab-
lished by X-ray crystallography. The perspective views
of the molecular structures of complexes 2–4 are shown
in Figs. 1–3. The central ruthenium atoms are all six-
coordinated in a slightly distorted octahedral geom-
etry. The Ru–S bond lengths in complex 2 ranging
from 2.396(2) to 2.454(3) Å agree well with those in the
related ruthenium(III) dialkyldithiophosphate species
[Ru{S2P(OMe)2}3] (2.396–2.452 Å), [Ru{S2P(OEt)2}3] (2.401–
2.425 Å) [14], and [Ru{S2P(OiPr)2}3] (2.398 and 2.420 Å) [29].
The S–Ru–S bond angles are 82.53(9)° and 81.48(12)°,
comparing well to those in the ruthenium(III) tri-dialky-
ldithiophosphate [Ru{S2P(OR)2}3] (81.12°–82.06°) [14, 29],
but are slightly larger than those in the ruthenium(II)
bi-diethyldithiophosphate cis-[Ru(CO)(PEt3){S2P(OEt)2}2]
(80.55(2)° and 80.34(2)°) [10]. The bite angles S–Ru–S in
complex 2 are also well in the range of those of other tran-
sition metal (Ir, Fe, Rh, Pt) complexes with the diisopro-
pyldithiophosphate ligand (79.86°–83.81°) [30–35]. The
Fig. 2:ꢀMolecular structure of the anion [RuCl2(κ2-N,O-L2)(CO)2]−
in 3, showing the atom labeling scheme and 40% displacement
ellipsoids. Hydrogen atoms and the counter cation are omitted
for clarity. Selected bond lengths (Å) and angles (deg): Ru(1)‒C(1)
1.857(4), Ru(1)‒C(2) 1.863(4), Ru(1)‒O(3) 2.059(2), Ru(1)‒N(1)
2.078(3), Ru(1)‒Cl(1) 2.4194(13), Ru(1)‒Cl(2) 2.4385(13), Cl(3)‒C(12)
1.740(3), O(1)‒C(1) 1.141(4), O(2)‒C(2) 1.125(4), O(3)‒C(3) 1.316(3),
N(1)‒C(9) 1.296(4); O(3)‒Ru(1)‒N(1) 89.65(9), Cl(1)‒Ru(1)‒Cl(2)
91.24(6), C(1)‒Ru(1)‒C(2) 91.35(14), C(2)‒Ru(1)‒Cl(2) 178.97(10),
N(1)‒Ru(1)‒Cl(1) 175.37(7), C(1)‒Ru(1)‒O(3) 173.75(13), O(1)‒C(1)‒
Ru(1) 177.3(3), O(2)‒C(2)‒Ru(1) 177.5(3).
Fig. 3:ꢀMolecular structure of the anion [RuCl2(κ2-N,O-L3)(CO)2]− in 4,
showing the atom labeling scheme and 40% displacement ellip-
soids. Hydrogen atoms and the counter cation are omitted for clarity.
Selected bond lengths (Å) and angles (deg): Ru(1)‒C(1) 1.856(2),
Ru(1)‒C(2) 1.865(2), Ru(1)‒O(3) 2.0662(14), Ru(1)‒N(1) 2.0840(15),
Ru(1)‒Cl(1) 2.4305(7), Ru(1)‒Cl(2) 2.4522(8), O(1)‒C(1) 1.133(2),
O(2)‒C(2) 1.137(3), O(3)‒C(3) 1.299(2), N(1)‒C(9) 1.297(3); O(3)‒Ru(1)‒
N(1) 90.37(6), Cl(1)‒Ru(1)‒Cl(2) 88.70(2), C(1)‒Ru(1)‒C(2) 89.83(10),
N(1)‒Ru(1)‒Cl(1) 175.44(5), C(2)‒Ru(1)‒O(3) 174.75(7), C(1)‒Ru(1)‒Cl(2)
176.32(6), O(1)‒C(1)‒Ru(1) 176.8(2), O(2)‒C(2)‒Ru(1) 178.8(2).
Fig. 1:ꢀMolecular structure of [Ru(κ2-N,O-L1){η2-S2P(OiPr)2}2]
2, showing the atom labeling scheme and 40% displacement
ellipsoids. Hydrogen atoms are omitted for clarity. Selected bond
lengths (Å) and angles (deg): Ru(1)‒O(1) 2.036(6), Ru(1)‒N(1)
2.121(6), Ru(1)‒S(2) 2.396(2), Ru(1)‒S(4) 2.397(3), Ru(1)‒S(1)
2.434(2), Ru(1)‒S(3) 2.454(3), S(1)‒P(1) 2.033(3), S(2)‒P(1) 2.011(3),
S(3)‒P(2) 2.016(6), S(4)‒P(2) 1.995(6), P(1)‒O(3) 1.565(7), P(1)‒O(2)
1.571(7), P(2)‒O(5) 1.553(10), P(2)‒O(4) 1.575(13), N(1)‒C(7)
1.309(11); O(1)‒Ru(1)‒N(1) 86.4(2), S(2)‒Ru(1)‒S(1) 82.53(9), S(4)‒
Ru(1)‒S(3) 81.48(12), S(1)‒Ru(1)‒S(3) 172.90(9), N(1)‒Ru(1)‒S(2)
172.54(18), O(1)‒Ru(1)‒S(4) 171.90(18).
Ru–N and Ru–O bond lengths in complex 2 are 2.121(6)
and 2.036(6) Å, respectively, with the chelate N–Ru–O
bond angle being 86.4(2)°. In related octahedral transition
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334ꢀ ꢀL.-H. Tang et al.: Structures of ruthenium complexes bidentate salicylaldiminato and dithiophosphato ligands
metal (Ti, Zr, V) complexes with the bidentate Schiff base Acknowledgment: This project was supported by the Nat-
L1 ligand, the chelate N–Ru–O bond angles range from ural Science Foundation of China (21372007).
77.77° to 88.11° [33, 34].
According to a CCDC search, up to now, there are
four reported structures of ruthenium carbonyl chlo-
ride complexes of the type [RuCl2(CO)2(κ2-N,O)], in which
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ꢂ335
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