The reactions between [RuHCl(CO)(PPh3)3] and quinoline carboxylic acids

Article abstract of DOI:10.1016/j.poly.2007.07.023

The reactions of [RuHCl(CO)(PPh₃)₃] with 8-hydroxy-2-methyl-quinoline-7-carboxylic acid and quinoline-2-carboxylic acid have been examined, and two novel ruthenium(II) complexes - [(PPh₃)₂RuH(CO)(C₁₀H

Full text of DOI:10.1016/j.poly.2007.07.023

Polyhedron 26 (2007) 5120–5130
www.elsevier.com/locate/poly
The reactions between [RuHCl(CO)(PPh3)3]
and quinoline carboxylic acids
a,
b
c
d
*
´
J.G. Małecki , R. Kruszynski , D. Tabak , J. Kusz
a
Department of Crystallography, Institute of Chemistry, University of Silesia, 9th Szkolna St., 40-006 Katowice, Poland
Department of X-Ray Crystallography and Crystal Chemistry, Institute of General and Ecological Chemistry, Ło´dz´ University of Technology,
b
_
116 Zeromski St., 90-924 Ło´dz´, Poland
c
Department of Organic Chemistry, Institute of Chemistry, University of Silesia, 9th Szkolna St., 40-006 Katowice, Poland
d
Institute of Physics, University of Silesia, 4th Uniwersytecka St., 40-006 Katowice, Poland
Revised 11 July 2007; accepted 12 July 2007
Available online 24 August 2007
Abstract
The reactions of [RuHCl(CO)(PPh3)3] with 8-hydroxy-2-methyl-quinoline-7-carboxylic acid and quinoline-2-carboxylic acid have
been examined, and two novel ruthenium(II) complexes – [(PPh3)2RuH(CO)(C10H8NO3)] and [(PPh3)2RuCl(CO)(C9H6O2)] – have been
obtained. The compounds have been studied by IR and UV–Vis spectroscopy, and X-ray crystallography. The molecular orbital dia-
grams of the complexes have been calculated with the density functional theory (DFT) method. The spin-allowed singlet–singlet elec-
tronic transitions of the compounds have been calculated with the time-dependent DFT method, and the UV–Vis spectra of the
compounds have been discussed on this basis.
ꢀ 2007 Elsevier Ltd. All rights reserved.
Keywords: Ruthenium; Quinoline carboxylic acid; Hydride and carbonyl complexes; X-ray structure; TDDFT method
1. Introduction
8-hydroxyquinoline pharmacophore seem especially inter-
esting. According to the results reported recently, some
new 8-hydroxyquinoline derivatives possess interesting
antifungal and herbicidal activities [18–20].
On the other hand ruthenium carbonyl and hydride
complexes are very interesting due to their catalytic and
structural properties. As it was shown for the complex with
quinoline 2-carboxylic acid, the formation of cis-coordi-
nated metal complexes is often a leading step in the cyto-
static processes involving metal based drugs [21].
In this paper we present the synthesis and characterisa-
tions of two novel ruthenium(II) complexes containing the
quinoline moiety.
The quinoline moiety is present in many classes of bio-
logically active compounds. A number of them have been
clinically used as antifungal, antibacterial and antiproto-
zoic drugs [1,2] as well as antituberculotic agents [3,4].
Some quinoline-based compounds show antineoplastic
activity [5]. Quinoline derivatives reveal also antiasthmatic
and antiplatelet activity [6–10] and due to acetylcholines-
terase inhibition, these compounds are potential drugs for
treatment of nervous diseases [11]. Recently strong atten-
tion has been focused on styrylquinoline derivatives
because of their activity as prospective HIV integrase
inhibitors [12–16]. The study dealing with styrylquinoline
derivatives showed that they could also possess strong
antifungal activity [17], thus the compounds containing
2. Experimental
2.1. Physical measurements
*
Corresponding author.
Infrared spectra were recorded on a Nicolet Magna 560
spectrophotometer in the spectral range 4000–400 cmꢀ1
E-mail addresses: gmalecki@us.edu.pl (J.G. Małecki), kruszyna@
´
p.lodz.pl (R. Kruszynski), tapcio@interia.pl (D. Tabak).
0277-5387/$ - see front matter ꢀ 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2007.07.023

J.G. Małecki et al. / Polyhedron 26 (2007) 5120–5130
5121
Table 1
Crystal data and structure refinement details of [(PPh3)2RuH(CO)(C10H8NO3)] Æ 0.5CH3OH (1) and [(PPh3)2RuCl(CO)(C9H6O2)] (2)
1
2
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
C49.50H45NO5.50P2Ru
904.88
293(2)
monoclinic
P21/n
C47H36ClNO3P2Ru
861.23
293(2)
monoclinic
P21/n
Unit cell dimensions
˚
a (A)
12.3516(5)
15.1962(5)
22.7646(9)
97.205(4)
4239.1(3)
4
1.418
0.496
10.9441(5)
21.2302(11)
16.8572(8)
92.153(4)
3913.9(3)
4
1.462
0.595
1760
˚
b (A)
˚
c (A)
b
3
˚
Volume (A )
Z
Dcalc (Mg/m3)
Absorption coefficient (mmꢀ1
F(000)
)
1868
Crystal dimensions (mm)
h Range for data collection (ꢁ)
Index ranges
0.08 · 0.08 · 0.28
2.83–25.00
0.04 · 0.12 · 0.38
2.91–25.00
ꢀ14 6 h 6 14, ꢀ8 6 k 6 18, ꢀ27 6 l 6 26
ꢀ7 6 h 6 13, ꢀ25 6 k 6 25, ꢀ20 6 l 6 20
Reflections collected
26145
24198
Independent reflections [Rint
Data/restraints/parameters
Goodness-of-fit on F2
]
7333 [0.0371]
7333/0/543
0.915
6860 [0.0467]
6860/0/496
0.977
Final R indices [I > 2r(I)]
R1 = 0.0338
R1 = 0.0267
wR2 = 0.0746
wR2 = 0.0627
R1 = 0.0467, wR2 = 0.0652
0.516 and ꢀ0.357
R indices (all data)
Largest difference in peak and hole (e A
R1 = 0.0669, wR2 = 0.0793
0.857 and ꢀ0.508
ꢀ3
˚
)
Fig. 1. Drawing of [(PPh3)2RuH(CO)(C10H8NO3)] Æ 0.5CH3OH with 50% probability displacement ellipsoids. The hydrogen atoms except H(1Ru) are
omitted.

5122
J.G. Małecki et al. / Polyhedron 26 (2007) 5120–5130
Fig. 2. Drawing of [(PPh3)2RuCl(CO)(C9H6O2)] with 50% probability displacement ellipsoids. The hydrogen atoms are omitted for clarity.
with the samples in the form of KBr pellets. Electronic
spectra were measured on a Lab Alliance UV–Vis 8500
spectrophotometer in the range 800–200 nm in dichloro-
methane solution. Elemental analyses (C, H, N) were per-
formed on a Perkin–Elmer CHN–2400 analyzer.
All reagents, except the 8-hydroxy-2-methylquinoline-7-
carboxylic acid, used for the synthesis of the complexes are
commercially available and were used without further
purification. The [RuHCl(CO)(PPh3)3] complex was syn-
thesised using a literature method [22]. The 8-hydroxy-2-
methylquinoline-7-carboxylic acid was synthesised as
described in the literature [13].
methanol (100 cmꢀ3) was refluxed until the solid dissolved,
then the solution was cooled and filtered. Crystals suitable
for X-ray crystal analysis were obtained by slow evapora-
tion of the reaction mixture. Yield 78% (1) and 82% (2).
Anal. Calc. for 1: C47H36ClNO3P2Ru: C, 63.94; H, 4.58;
N, 3.64. Found: C, 64.01; H, 4.53; N, 3.66%.
2: C50H42ClNO3P2Ru: C, 66.48; H, 4.69; N, 1.55.
Found: C, 66.28; H, 4.59; N, 1.51%.
IR (KBr, cmꢀ1): 1: 3055 mCH; 2925 mCH–phenyl; 1945 mRu–H
1918 mCO; 1610 mCN; 1590 asmCOO; 1482 d(C–CH in the plane)
;
;
;
1436 mPh(P–Ph)
996 d(C–C out of the plane)
d(C–C in the plane)
2: 3060 mCH; 1938 mCO; 1650 mCN; 1596 asmCOO; 1482
d(C–CH in the plane) 1434 mPh(P–Ph) 1348 smCOO 1089
(C–CH in the plane); 750 d(C–C out of the plane); 696 d(C–C in the plane)
UV–Vis [nm] in CH3OH (loge): 1: 400 (3.48); 357 sh
;
1378 smCOO
;
1121 d(C–CH in the plane)
;
756 d(C–C out of the plane)
;
697
.
2.2. Synthesis of [(PPh3)2RuH(CO)(C10H8NO3)] (1)
and [(PPh3)2RuCl(CO)(C9H6O2)] (2)
;
;
;
d
.
A
suspension of [RuHCl(CO)(PPh3)3] (0.95 g,
1 · 10ꢀ3 mol) and 8-hydroxy-2-methyl-quinoline-7-carbox-
(3.59); 332 (3.77); 281 (4.31); 210 (4.40).
ylic acid (0.21 g) or quinoline-2-carboxylic acid (0.18 g) in
2: 350 (3.01); 283 (3.38); 238 (4.20); 206 (4.32).
CO
Cl
HOOC
N
CH3
N
Ru
PPh3
PPh3
O
Ph3P
Ru
H
PPh3
CO
C
O
O
Fig. 3. Structural drawing of [(PPh3)2RuH(CO)(C10H8NO3)].
Fig. 4. Structural drawing of [(PPh3)2RuCl(CO)(C9H6O2)].

J.G. Małecki et al. / Polyhedron 26 (2007) 5120–5130
5123
Fig. 5. Part of the molecular packing of [(PPh3)2RuH(CO)(C10H8NO3)].
2.3. DFT calculations
atoms: 6–31g(2d,p) – chlorine, 6–31g** – carbon, nitrogen,
oxygen, and 6–31g(d,p) – hydrogen. Natural bond orbital
(NBO) calculations were performed using the NBO code
[28] included in GAUSSIAN-03.
The GAUSSIAN-03 program [23] was used for the calcula-
tions. The geometry optimisation was carried out using the
DFT method with the B3LYP functional [24,25]. The elec-
tronic transitions were calculated with the PCM model [26]
with dichloromethane as the solvent. The calculation was
performed using the DZVP basis set [27] with f functions
and with exponents 1.94722036 and 0.748930908 on the
ruthenium atom and polarisation functions for all other
2.4. Crystal structure determination and refinement
A green prism of complex 1 and a white prism of 2 were
mounted in turn on a KM-4-CCD automatic diffractome-
ter equipped with a CCD detector, and were used for data

5124
J.G. Małecki et al. / Polyhedron 26 (2007) 5120–5130
Fig. 6. Part of the molecular packing [(PPh3)2RuCl(CO)(C9H6O2)].
collection. X-ray intensity data were collected with graphite
monochromated Mo Ka radiation (k = 0.71073 A) at the
hydrogen atoms were found from difference Fourier syn-
thesis after four cycles of anisotropic refinement, and
refined as ‘‘riding’’ on the adjacent atom with an individual
isotropic temperature factor equal to 1.2 times the value of
the equivalent temperature factor of the parent atom. The
H(1Ru) atom in complex 1 was placed in a calculated posi-
˚
temperature 295.0(3) K, with the x scan mode. The Ewald
sphere reflections were collected up to 2h = 50.0ꢁ for both
complexes. The unit cell parameters were determined from
least-squares refinement of the setting angles of 7333 and
6860 strongest reflections for complexes 1 and 2, respec-
tively. Details concerning the crystal data and refinement
are gathered in Table 1. The reference frames, monitored
every 40 measurement frames, show 1.01% decay for the
crystal of compound 1 and no decay for the crystal of com-
pound 2. During the data reduction of compound 1 a decay
correction was taken into account. Lorentz, polarisation
and numerical absorption [29] corrections were applied.
The structures were solved using the Patterson method
combined with a partial structure expansion procedure.
All the non-hydrogen atoms were refined anisotropically
using the full-matrix, least-squares technique on F2. The
˚
tion (Ru–H distance 1.6 A) according to similar com-
pounds [30–36]. SHELXS97 [37], SHELXL97 [38] and SHELXTL
[39] programs were used for all calculations. Atomic scat-
tering factors had values incorporated in the computer
programs.
3. Results and discussion
The reaction between the [RuHCl(CO)(PPh3)3] complex
and 8-hydroxy-2-methyl-quinoline-7-carboxylic acid or
quinoline-2-carboxylic acid in methanolic solution gives
the mononuclear ruthenium(II) compounds [(PPh3)2RuH-

J.G. Małecki et al. / Polyhedron 26 (2007) 5120–5130
5125
(CO)(C10H8NO3)] (green, air-stable, crystalline solid) and
[(PPh3)2RuCl(CO)(C9H6O2)] (white solid). Infrared spectra
of the complexes exhibit characteristic bands of coordi-
nated ligands – quinoline carboxylic acid, CO, PPh3 and
the hydride group.
and molecular packing is depicted, receptively, in Figs. 5
and 6. The ruthenium atom in the complex [(PPh3)2RuH-
(CO)(C10H8NO3)] is in a distorted octahedral environment
with trans-triphenylphosphine ligands (angle P(1)–Ru(1)–
P(2) 172.19(3)ꢁ). The carbonyl ligand is in a trans-position
to the O donor atom (C(1)–Ru(1)–O(4) 178.12(11)ꢁ) and
the hydrido ion lies trans to the coordinated nitrogen from
the quinoline ligand – with an angle of 170.0ꢁ. The Ru–N
bond distance is longer in complex 1 than in complex 2
due to the trans effect of the hydride ligand. The inter-
atomic distances in the carbonyl and triphenylphosphine
ligands are normal.
The strong bands at 1938 and 1918 cmꢀ1 for complex 1
and 2, respectively, are assigned to the mCO stretching vibra-
tions of the ruthenium bonded carbonyl group, and the
band at 1945 cmꢀ1 corresponds to mRu–H of the hydride
ligand (complex 1). The mCO and mRu–H stretching vibra-
tions in the [RuHCl(CO)(PPh3)3] complex are at 2020
and 1903 cmꢀ1, respectively. The bands at 1610 and
1650 cmꢀ1 are attributed to the CN stretching vibration
of the quinoline ligand. The asymmetric and symmetric
mCOO stretching bands are at 1590, 1596 cmꢀ1 and 1378,
1348 cmꢀ1 for compounds 1 and 2, respectively.
The positions of the mCO and mRu–H bands in the IR spec-
trum of complex 1 indicate a decrease of the metal–car-
bonyl carbon interaction and an increase of the Ru–H
bond order. Taking into account the IR spectra of both
complexes, the quinoline type ligand is a r-donor that
induces a large Ru–CO back-bonding.
In the structure of compound 1 one very weak intramo-
lecular O(4)–HO(3) hydrogen bond (Dꢁ ꢁ ꢁA distance
˚
2.554(3) A and D–Hꢁ ꢁ ꢁA angle 151.7ꢁ) and one very weak
intermolecular C(40)–H(40)O(98) hydrogen bond (Dꢁ ꢁ ꢁA
˚
distance 3.290(10) A and D–Hꢁ ꢁ ꢁA angle 139.5ꢁ) can be
found.
The ruthenium atom of complex 2, [(PPh3)2RuCl(CO)-
(C9H6O2)], is also in a distorted octahedral environment
with cis-triphenylphosphine ligands (angle P–Ru–P
99.28(2)ꢁ). The carbonyl ligand is in a trans position to
the carboxylic O donor atom (O(2)–Ru–C(19) 174.95(9)ꢁ)
and the chloride ion is trans to the P(2) atom
ꢀ166.11(2)ꢁ. All Ru–ligand distances, namely Ru–Cl
2.4250(6), Ru–P 2.3763(7), 2.3861(7), Ru–N 2.169(2),
3.1. Crystal structure
Both obtained complexes crystallise in the monoclinic
space group P21/n. The crystal data of complexes 1 and 2
are given in Table 1. The molecular structures of 1 and 2
are presented in Figs. 1 and 2 (see Figs. 3, 4), respectively,
˚
Ru–C 1.826(3) and Ru–O 2.1035(16) A, are normal and
comparable with distances in other ruthenium complexes
containing heterocyclic ligands.
Table 2
Selected bond lengths (A) and angles (ꢁ) for [(PPh3)2RuH(CO)(C10H8NO3)] (1) and [(PPh3)2RuCl(CO)(C9H6O2)] (2)
˚
1
2
Experimental
Calculated
Experimental
Calculated
˚
Bond lengths (A)
Ru(1)–C(1)
Ru(1)–O(4)
Ru(1)–N(1)
Ru(1)–P(2)
Ru(1)–P(1)
Ru(1)–H(1Ru)
C(1)–O(1)
1.805(4)
2.127(19)
2.221(3)
2.355(8)
2.360(8)
1.6042
1.806
2.126
2.225
2.354
2.361
1.604
1.159
Ru(1)–C(19)
Ru(1)–O(2)
Ru(1)–N(1)
Ru(1)–P(2)
Ru(1)–P(1)
Ru(1)–Cl(3)
C(19)–O(1)
1.826(3)
2.1035(16)
2.169(2)
2.3861(7)
2.3763(7)
2.4250(6)
1.155(3)
1.865
2.108
2.243
2.456
2.438
2.458
1.164
1.231(4)
Angles (ꢁ)
C(1)–Ru(1)–O(4)
C(1)–Ru(1)–N(1)
O(4)–Ru(1)–N(1)
C(1)–Ru(1)–P(2)
O(4)–Ru(1)–P(2)
N(1)–Ru(1)–P(2)
C(1)–Ru(1)–P(1)
O(4)–Ru(1)–P(1)
N(1)–Ru(1)–P(1)
P(2)–Ru(1)–P(1)
C(1)–Ru(1)–H(1Ru)
O(4)–Ru(1)–H(1Ru)
N(1)–Ru(1)–H(1Ru)
P(2)–Ru(1)–H(1Ru)
P(1)–Ru(1)–H(1Ru)
178.12(11)
103.76(12)
75.66(9)
92.83(10)
89.02(6)
97.25(6)
86.66(10)
91.55(6)
90.44(6)
172.19(3)
85.4
178.14
103.67
75.83
92.87
88.97
97.33
86.68
91.53
90.44
172.10
85.30
95.09
170.21
85.99
86.12
C(19)–Ru(1)–O(2)
N(1)–Ru(1)–C(19)
O(2)–Ru(1)–N(1)
P(1)–Ru(1)–C(19)
P(1)–Ru(1)–O(2)
N(1)–Ru(1)–P(1)
C(19)–Ru(1)–P(2)
O(2)–Ru(1)–P(2)
N(1)–Ru(1)–P(2)
P(2)–Ru(1)–P(1)
C(19)–Ru(1)–Cl(3)
O(2)–Ru(1)–Cl(3)
N(1)–Ru(1)–Cl(3)
P(1)–Ru(1)–Cl(3)
P(2)–Ru(1)–Cl(3)
174.95(9)
98.15(10)
77.43(7)
84.89(8)
99.05(5)
169.76(6)
99.86(8)
82.70(5)
89.87(6)
99.28(2)
92.45(8)
84.56(5)
81.98(6)
88.14(2)
166.11(2)
178.18
101.67
76.57
87.79
94.03
163.87
97.02
82.57
90.77
101.11
93.27
86.92
80.28
86.21
167.56
95.1
170.0
86.1
86.1

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J.G. Małecki et al. / Polyhedron 26 (2007) 5120–5130
The molecules in the crystal are connected by four very
3.3. Charge distribution and NBO analysis
weak C–Hꢁ ꢁ ꢁO intramolecular hydrogen bonds: C(12)–
˚
H(12)ꢁ ꢁ ꢁO(2) (Dꢁ ꢁ ꢁA distance 3.059(3) A, D–Hꢁ ꢁ ꢁA angle
The calculated charges on the ruthenium atom in the
studied complexes are considerable lower than the formal
charge of +2 and are close to ꢀ0.01 and 0.26 for 1 and
2, respectively. The charges on the P atoms are positive
and close to 1.15 (1.20); the charge on the chloride
ligand in [(PPh3)2RuCl(CO)(C9H6O2)] is larger than ꢀ1
(ꢀ0.55), the charge on the quinoline carboxylic acid
ligands is close to ꢀ0.64 for 1 and ꢀ0.52 for 2. The
occupancies of the ruthenium d orbitals, obtained from
the NBO analysis, are as follow: dxy ꢀ 1.73; dxz ꢀ 1.84;
˚
120.0ꢁ), C(21)–H(21)ꢁ ꢁ ꢁO(2) (Dꢁ ꢁ ꢁA distance 3.074(3) A,
D–Hꢁ ꢁ ꢁA 145.6ꢁ), C(6)–H(6)ꢁ ꢁ ꢁCl(3) (Dꢁ ꢁ ꢁA distance
˚
3.208(3) A, D–Hꢁ ꢁ ꢁA angle 108.90ꢁ) and C(43)–
˚
H(43)ꢁ ꢁ ꢁO(1) (Dꢁ ꢁ ꢁA distance 3.267(4) A, D–Hꢁ ꢁ ꢁA angle
132.6ꢁ).
3.2. Geometry optimisation
The geometries of the studied complexes were optimised
by the DFT method with the B3LYP functional. The
geometry parameters for the optimised complexes are gath-
ered in Table 2. In general, the predicted bond lengths and
angles are in agreement with the X-ray structural data. The
largest difference is found for the C(1)–O(1) bond
2
dyz ꢀ 1.21; dx2ꢀy ꢀ 1.23; dz2 ꢀ 1.61 for [(PPh3)2RuH-
(CO)(C10H8NO3)] and dxy ꢀ 1.80; dxz ꢀ 1.74; dyz ꢀ 1.75;
2
dx2ꢀy ꢀ 1.13; dz2 ꢀ 0.96 for [(PPh3)2RuCl(CO)(C9H6O2)].
The Ru–C bond orbitals in the two studied complexes
are polarised towards the carbon atom, and the C„O
bond orbitals are polarised towards the oxygen end.
The oxygen atoms of the carbonyl ligands have one lone
pair (LP) orbital. The occupancies of the Ru–C bonds
are (anti-bonding NBOs are given in round brackets)
˚
(ꢂ0.072 A) (compound 1). The maximum differences
between the optimised and experimental geometry of com-
˚
pound 2 are exhibited in the Ru(1)–N(1) distance (0.074 A)
and N(1)–Ru(1)–P(1) angle (5.9ꢁ).
Table 3
The energy and character of selected occupied and virtual MOs for [(PPh3)2RuH(CO)(C10H8NO3)] (1) and [(PPh3)2RuCl(CO)(C9H6O2)] (2)
[(PPh3)2RuH(CO)(C10H8NO3)] (1) [(PPh3)2RuCl(CO)(C9H6O2)] (2)
E (eV)
Character
qu + nP
pqu
E (eV)
Character
Cl + nP
pCl
pPh
pPh
HOMO ꢀ 20
HOMO ꢀ 19
HOMO ꢀ 18
HOMO ꢀ 17
HOMO ꢀ 16
HOMO ꢀ 15
HOMO ꢀ 14
HOMO ꢀ 13
HOMO ꢀ 12
HOMO ꢀ 11
HOMO ꢀ 10
HOMO ꢀ 9
HOMO ꢀ 8
HOMO ꢀ 7
HOMO ꢀ 6
HOMO ꢀ 5
HOMO ꢀ 4
HOMO ꢀ 3
HOMO ꢀ 2
HOMO ꢀ 1
HOMO
ꢀ7.902
ꢀ7.788
ꢀ7.393
ꢀ7.306
ꢀ7.249
ꢀ7.200
ꢀ7.067
ꢀ6.999
ꢀ6.983
ꢀ6.966
ꢀ6.893
ꢀ6.860
ꢀ6.787
ꢀ6.776
ꢀ6.708
ꢀ6.669
ꢀ6.615
ꢀ6.400
ꢀ6.313
ꢀ5.886
ꢀ5.255
ꢀ1.567
ꢀ0.838
ꢀ0.759
ꢀ0.631
ꢀ0.571
ꢀ0.484
ꢀ0.272
ꢀ0.179
ꢀ0.160
ꢀ0.098
0.041
p
ꢀ7.728
ꢀ7.510
ꢀ7.282
ꢀ7.219
ꢀ7.203
ꢀ7.099
ꢀ7.061
ꢀ7.040
ꢀ6.949
ꢀ6.931
ꢀ6.865
ꢀ6.838
ꢀ6.819
ꢀ6.770
ꢀ6.721
ꢀ6.675
ꢀ6.596
ꢀ6.588
ꢀ6.487
ꢀ6.248
ꢀ6.119
ꢀ2.025
ꢀ1.518
ꢀ0.999
ꢀ0.882
ꢀ0.811
ꢀ0.713
ꢀ0.555
ꢀ0.539
ꢀ0.433
ꢀ0.248
ꢀ0.218
ꢀ0.174
ꢀ0.063
ꢀ0.052
p
p
qu + rH
pphosphine
pphosphine
pCOOH
pPh
pPh
pPh
pPh
pPh
pPh
pPh
p
p
p
p
qu + pCl
Ph + pCOO
Cl + pPh
COO + d
pPh
pPh
pPh
pPh
pPh
pPh
pPh
p
p
p
Ph + d + pCO
Ph + d + pCO
Ph + d
pPh + d + pCO
pPh
pPh
d + pCO + nP
d + p*CO
d + nP
d + p*qu
p*qu
p
p
Ph + d + pCO
Cl + pqu
d + p*ClpCo
d + p*Cl
p*qu
LUMO
LUMO + 1
LUMO + 2
LUMO + 3
LUMO + 4
LUMO + 5
LUMO + 6
LUMO + 7
LUMO + 8
LUMO + 9
LUMO + 10
LUMO + 11
LUMO + 12
LUMO + 13
dz2 + p*qu
p*qu + p*Ph
d + p*Ph
d + p*Ph
p*Ph
d ꢀ rCl ꢀ np
p*qu
d + p*qu
d + p*Ph
p*Ph
p*Ph
p*Ph
p*Ph
p*Ph
p*Ph
d + p*CO + p*Ph
d + p*CO + p*Ph
p*Ph + p*CO
d + p*CO + p*Ph
p*Ph
p*Ph
p*Ph
0.065
0.201
0.234
p*Ph
d + p*CO + p*Ph
d + p*CO + p*Ph
p*Ph

J.G. Małecki et al. / Polyhedron 26 (2007) 5120–5130
5127
for complex 1: 1.976 (0.398) and for complex 2: 1.938
(0.272).
atom possesses a d6 configuration. The highest MO is
dxz with a contribution of the pp antibonding orbitals
from the quinoline ligand in the case of complex 1 and
from the chlorine ligands of compound 2. The pRu–CO
bonding interaction contribute in the H-2 and H-3 orbi-
tals of compounds 1 and 2. The p*Ru–CO orbitals are also
distributed among several unoccupied molecular orbitals.
They contribute in L + 12, L + 13 (complex 1) and
L + 9, L + 11 for 2. The LUMO orbitals are localised
on the quinoline ring. The dz2 orbital of the Ru atom
3.4. Electronic structure
The energies and characters of several highest occu-
pied and lowest unoccupied molecular orbitals of the
studied complexes are presented in Table 3. The
HOMO–LUMO gaps of complexes 1 and 2 are 3.69
and 4.09 eV, respectively. In both cases, the ruthenium
3.0
2.0
1.0
0.0
400.0
300.0
Wavelength, nm
200.0
220 230 240 250 260 270 280 290 300 310 320 330 340 350 360 370 380 390 400
Wavelength, nm
Fig. 7. The UV–Vis spectra of [(PPh3)2RuH(CO)(C10H8NO3)]: (a) experimental; (b) calculated.

5128
J.G. Małecki et al. / Polyhedron 26 (2007) 5120–5130
makes the largest contribution into L + 3, whereas the
L + 4 molecular orbital has dx2ꢀy character in the stud-
ied complexes.
method, are presented in Figs. 7 and 8, respectively, for
complexes 1 and 2. The contour of the calculated spectrum
was broadening by the Lorentzian function, calculated by
the equation:
2
3.5. Electronic spectrum
I0
I ¼
;
where
2
mꢀm0
1 þ ð
Þ
c
The experimental and calculated electronic spectra of
allowed singlet transitions, calculated with the TDDFT
c ¼ 1=2 the spectral width at 1=2 height:
2.0
1.5
1.0
0.5
0.0
200.0
300.0
400.0
500.0
Wavelength, nm
220
240
260
280
300
320
340
360
380
400
420
440
Wavelength, nm
Fig. 8. The UV–Vis spectra of [(PPh3)2RuCl(CO)(C9H6O2)]: (a) experimental; (b) calculated.

J.G. Małecki et al. / Polyhedron 26 (2007) 5120–5130
5129
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experimental bands are based on the criterion of the energy
and oscillator strength of the calculated transitions. In the
description of the electronic transitions only the main com-
ponents of the molecular orbitals are taken into
consideration.
The first experimental bands at 400 and 357 nm in
[(PPh3)2RuH(CO)(C10H8NO3)] (1) and at 350.0 nm in
[(PPh3)2RuCl(CO)(C9H6O2)] (2) consist of d ! p*qu MLCT
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pCl ! p*Ph; pCO ! p P*h; pCO ! pq*u). The bands at 210
and 206 nm for complexes 1 and 2, respectively, were not
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Acknowledgement
The crystallographic part was financed by funds allo-
cated by the Ministry of Science and Higher Education
to the Department of X-ray Crystallography and Crystal
Chemistry, Institute of General and Ecological Chemistry,
´ ´
Technical University of Łodz.
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Appendix A. Supplementary material
CCDC 649418 and 649903 contain the supplementary
crystallographic data for 1 and 2. These data can be
obtained free of charge via http://www.ccdc.cam.ac.uk/
conts/retrieving.html, or from the Cambridge Crystallo-
graphic Data Centre, 12 Union Road, Cambridge CB2
1EZ, UK; fax: (+44) 1223-336-033; or e-mail: deposit@
ccdc.cam.ac.uk.
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