Studies on the reactions of ruthenium(II) substrates with tridentate (N,N,O) azo ligands

Article abstract of DOI:10.1016/j.ica.2010.04.016

Reactions of 1-{[2-(arylazo)phenyl]iminomethyl}-2-phenol, HL_sal, 1, [where H represents the dissociable protons upon complexation and aryl groups of HL_sal are phenyl for HL¹_sal, p-methylphenyl for HL²

Full text of DOI:10.1016/j.ica.2010.04.016

Inorganica Chimica Acta 363 (2010) 2865–2873
Contents lists available at ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Studies on the reactions of ruthenium(II) substrates with tridentate (N,N,O)
azo ligands
Poulami Pattanayak a, Debprasad Patra a, Jahar Lal Pratihar a, Andrew Burrows b, Mary F. Mahon b,
Surajit Chattopadhyay a,
*
a Department of Chemistry, University of Kalyani, Kalyani 741235, India
b Department of Inorganic Chemistry, University of Bath, Claverton Down, Bath BA27AY, UK
a r t i c l e i n f o
a b s t r a c t
Article history:
Reactions of 1-{[2-(arylazo)phenyl]iminomethyl}-2-phenol, HLsal, 1, [where H represents the dissociable
protons upon complexation and aryl groups of HLsal are phenyl for HL1sal, p-methylphenyl for HL2sal, and
Received 29 January 2010
Received in revised form 5 April 2010
Accepted 8 April 2010
p-chlorophenyl for HL3sal], ligands with Ru(H)(CO)(Cl)(PPh3)3 afforded complexes of composition
ꢀ
[(Lsal)Ru(CO)(Cl)(PPh3)] and (Lsal)2Ru where the N,N,O donor tridentate (Lsal
)
ligands coordinated the
Available online 18 April 2010
metal centre facially and meridionally, respectively. Stepwise formation of [(Lsal)2Ru] has been
ascertained. Reaction of 1-{[2-(arylazo)phenyl]iminomethyl}-2-napthol, HLnap, 2, [where H represents
the dissociable protons upon complexation and aryl groups of HLnap are phenyl for HL1nap, p-methyl-
phenyl for HL2nap, and p-chlorophenyl for HL3nap], ligands with Ru(H)(CO)(Cl)(PPh3)3 afforded exclusively
Dedicated to Animesh Chakravorty
Keywords:
Facial
the complexes of composition [(Lnap)Ru(CO)(Cl)(PPh3)], where N,N,O donor tridentate (Lnap)
ꢀ was facially
coordinated. The ligand 1-{[2-(phenylazo)phenyl]aminomethyl}-2-phenol, HL, 3, was prepared by reduc-
ing the aldimine function of HL1sal. Reaction of HL with Ru(PPh3)3Cl2 afforded new azosalen complex of
Ru(III) in concert with regiospecific oxygenation of phenyl ring of HL. All the new ligands were charac-
terized by analytical and spectroscopic techniques. The complexes were characterized by analytical
and spectroscopic techniques and subsequently confirmed by the determination of X-ray structures of
selected complexes.
Meridional
Azo ligands
(N,N,O) donor
Oxygenation
Ó 2010 Elsevier B.V. All rights reserved.
1. Introduction
their catalytic and biological activity [7]. Ruthenium complexes
based upon a tripodal phosphine ligand are used as catalysts for
The ligands which bind the transition metal ion in a predictable
way play important role in modern coordination chemistry since
they may determine the reactive sites available at a metal centre
and modulate their reactivity. Although several kinds of azo li-
gands have been utilized to explore the coordination chemistry
of transition metal ions but (N,N,O) donor azo ligands are scarce
[1]. Therefore we paid attention to design and synthesis new
(N,N,O) donor azo ligands as given in Chart 1.
Moreover, coordination chemistry of ruthenium incorporating
(N,N,O) donor azo ligands have received only marginal attention
[2]. Tridentate ligands may bind the transition metal ion either
meridionally or facially in octahedral complexes. 1,4,7 tri aza
cyclononane; 1,4,7 trithia cyclononane; tris pyrazolyl borate and
a few scorpionate and tripodal ligands are good examples of fa-
cially coordinating ligands [3–6]. Fascinating chemistry of such
metal complexes have enhanced the interest on the synthesis of
new tridentate ligands that have potential to bind the metal centre
facially. Facially capped complexes have received attention due to
conversion of dimethyl oxalate to ethylene glycol [8]. Homoge-
neously-catalysed hydrogenation of esters to yield alcohols is also
known to occur using the facially capped ruthenium complexes as
catalyst [9–11].
Herein, we have described the reactions of appropriate ruthe-
nium substrates with HLsal and HLnap. The conditions to obtain Ru(II)
complexes incorporating facially and meridionally coordinated tri-
dentate (N,N,O) donor azo ligands have been described. Reaction
of new HL ligands with Ru(II) substrate resulting regiospecific oxy-
genation of phenyl ring of HL, with concomitant formation of new
azosalen complex of Ru(III) have been delineated in this paper.
2. Results and discussion
2.1. Syntheses
The 1-{[2-(arylazo)phenyl]iminomethyl}-2-phenol ligands were
prepared by the condensation of salicylaldehyde with 2-(arylazo)
aniline as reported earlier [12]. These ligands are abbreviated as
HLsal [where aryl groups of HLsal are phenyl for HL1sal, p-methyl
* Corresponding author. Tel.: +91 33 25828750; fax: +91 33 25828282.
E-mail address: scha8@rediffmail.com (S. Chattopadhyay).
0020-1693/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2010.04.016

2866
P. Pattanayak et al. / Inorganica Chimica Acta 363 (2010) 2865–2873
R
N
R
HO
HO
N
HO
N
N
N
N
N
N
N
H
2
3
HL
1
HLsal
HLnap
Chart 1.
phenyl for HL2 and p-chloro phenyl for HL3sal, H represents the
dissociable phenolic proton] in this paper.
Reaction of one equivalent Ru(H)(CO)(Cl)(PPh3)3 with two equiv-
alent HLsal in refluxing toluene afforded [(Lsal)Ru(CO)(PPh3)(Cl)], 4,
and [(Lsal)2Ru], 5, in ꢁ60% and ꢁ20% yields, respectively after 8 h
as shown in Eq. (1).
the major product in presence of excess ligand and upon extension
of reaction time to ꢁ24 h. On the other hand, the [(Lsal)Ru(-
CO)(Cl)(PPh3)] products were major even after prolonged reflux
when the ligand was taken in equivalent amount with respect to
the ruthenium substrate. Subsequently, the conversion of [(Lsal)-
Ru(CO)(Cl)(PPh3)] into [(Lsal)2Ru] occurred upon reaction of HLsal
with [(Lsal)Ru(CO)(Cl)(PPh3)] in refluxing toluene signifying the
stepwise formation of [(Lsal)2Ru] according to the sequence as
shown in Scheme 1.
sal
R
Cl
Ph3P
Summarily, the HLsal ligands bind the metal centre facially as
well as meridionally forming two types of complexes, [(Lsal)Ru
(CO)(Cl)(PPh3)] and [(Lsal)2Ru]. Moreover, formation of [(Lsal)2Ru]
upon treatment of [(Lsal)Ru(CO)(Cl)(PPh3)] with HLsal was signifi-
cant in terms of the lability of [(Lsal)Ru(CO)(Cl)(PPh3)] with re-
spect to ligand substitution along with concomitant geometrical
isomerisation. As a result attention was drawn to examine the
reactions of Ru(H)(CO)(Cl)(PPh3)3 with the ligands that are bulk-
ier than HLsal. The bulkier ligands HLnap, 2, were designed and
synthesized keeping the nature of coordinating sites similar to
Ru(H)(CO)(Cl)(PPh3)3
HO
N
CO
N
R
Ru
N
Toluene
Reflux
N
O
N
N
1
4
HLsal
[(Lsal)Ru(CO)(Cl)(PPh3)]
O
N
N
N
Ru
N
HLsal
The new ligand, 1-{[2-(arylazo)phenyl]iminomethyl}-2-nap-
thol, HLnap 2, [where aryl groups of HLnap are phenyl for
HL1nap; p-methyl phenyl for HL2
.
O
+
N
R
N
R
,
and p-chloro phenyl for
nap
HL3nap] were prepared by refluxing appropriate 2-(arylazo)aniline
with 2-hydroxy-1-naphthaldehyde in diethyl ether as shown in
Eq. (2).
5
ð1Þ
[(Lsal)2Ru]
R
Compound
R
HL1
H
1a
1b
1c
4a
sal
OH
CHO
HL2
CH3
sal
+
HL3
N
sal
Cl
N
[(L1sal)Ru(CO)(Cl)(PPh3)]
[(L2sal)Ru(CO)(Cl)(PPh3)]
H
NH2
4b
CH3
Cl
[(L3sal)Ru(CO)(Cl)(PPh3)]
[(L1sal)2Ru]
4c
5a
5b
ð2Þ
R
H
[(L2sal)2Ru]
CH3
HO
Et2O
[(L3sal)2Ru]
5c
Cl
N
N
N
Reflux
The HLsal ligands coordinated Ru(II) centre dissociating the phe-
nolic proton in both the complexes, [(Lsal)Ru(CO)(PPh3)(Cl)] and
[(Lsal)2Ru]. Indeed the tridentate N,N,O donor anionic (Lsal)
ꢀ species
are held facially and meridionally in the coordination sphere of
[(Lsal)Ru(CO)(Cl)(PPh3)] and [(Lsal)2Ru], respectively (X-ray struc-
ture, see below). The bis complexes, [(Lsal)2Ru], were obtained as
2
HLnap

P. Pattanayak et al. / Inorganica Chimica Acta 363 (2010) 2865–2873
2867
Ru(H)(CO)(Cl)(PPh3)3
+
[(Lsal)Ru(CO)(Cl)(PPh3)]
HLsal
HLsal
PPh3
O
N
O
N
OH
N
HO
N
[(Lsal)Ru(CO)(Cl)(PPh3)]
+
[(Lsal)2Ru]
Ru
Cl
N
N
Scheme 1.
R
N
Ph3P
Cl
CO
7
8
Ru(H)(CO)(Cl)(PPh3)3
Ru
HO
N
O
N
Toluene
N
N
R
Reflux
During the reaction, the reduced aldimine form of HL was oxidized
to the parent imine form with concomitant oxygenation at the ortho
carbon of the phenyl ring of phenylazo fragment. It was believed
that the two hard phenolic O donors of the oxygenated ligand sta-
bilized the Ru(III).
N
2
6
[(Lnap)Ru(CO)(Cl)(PPh3)]
R
HLnap
Compound
HL1
2a
H
2.2. Characterization
CH3
Cl
2b
HL2nap
HL3nap
2c
nap
[(L1nap)Ru(CO)(Cl)(PPh3)]
[(L2nap)Ru(CO)(Cl)(PPh3)]
[(L3nap)Ru(CO)(Cl)(PPh3)]
The UV–Vis spectra of The [(Lsal)Ru(CO)(Cl)(PPh3)] and
[(Lnap)Ru(CO)(Cl)(PPh3)] complexes in dichloromethane solution
exhibited characteristic absorptions near 440 and 340 nm. The
bis complexes [(Lsal)2Ru] exhibited absorption near 630 nm.
H
6a
CH3
6b
6c
Cl
ð3Þ
Reaction of Ru(H)(CO)(Cl)(PPh3)3 with the ligand system HLnap
in refluxing toluene yielded only one product of composition
[(Lnap)Ru (CO)(Cl)(PPh3)], 6, as given in Eq. (3) where the anionic
tridentate (N,N,O) ligands, (Lnap)ꢀ, bind the metal centre facially.
It is important to note that the reaction of [(Lnap)Ru(CO)(Cl)(PPh3)]
with HLnap or the reaction of Ru(H)(CO(Cl)(PPh3)3 with excess
HLnap in refluxing toluene did not afford the bis complex
[(Lnap)2Ru] justifying the exclusive formation of [(Lnap)Ru
(CO)(Cl)(PPh3)]. It was anticipated that either the bulkier ligand
system did not allow another HLnap within the coordination sphere
due to steric hindrance or the nature of HLnap ligand itself was not
suitable for further substitution. Thus, formation of Ru(II) com-
plexes incorporating facially coordinated (N,N,O) donor azo li-
gands, HLsal and HLnap, depend on the ligand system, ligand to
metal substrate stoichiometric ratio and reaction time. Since HLsal
and HLnap ligands are conjugated and more rigid than the noncon-
jugated ligand systems so it was contemplated to introduce flexi-
bility within such ligand backbones by reducing the aldimine
functions into corresponding dihydro form. Therefore, new ligand
system 1-{[2-(phenylazo)phenyl]aminomethyl}-2-phenol, HL, 3,
Fig. 1. UV–Vis spectra of [(L1sal)Ru(CO)(Cl)(PPh3) (—), [(L1nap)Ru(CO)(Cl)(PPh3)]
(–d–d–) and [(L1sal)2Ru ] (- - -) in dichloromethane solution.
was prepared by reducing the HL1 with sodium borohydride in
sal
methanol as shown in Eq. (4). The ligand HL was characterized
unequivocally from its spectral data (see below).
HO
HO
HN
N
N
N
NaBH4
MeOH
N
N
3
ð4Þ
Reaction of HL with Ru(H)(CO(Cl)(PPh3)3 in refluxing toluene
did not afford any isolable product. Therefore the metal substrate
Ru(PPh3)3Cl2 was chosen arbitrarily to carry out reaction with li-
gand HL. Upon refluxing Ru(PPh3)3Cl2 with HL in toluene afforded
new Ru(III) complex [(OL)Ru(PPh3)Cl], 7, where H2OL is shown in 8.
Fig. 2. UV–Vis spectra of 3 (—), and 7 (- - -) in dichloromethane solution.

2868
P. Pattanayak et al. / Inorganica Chimica Acta 363 (2010) 2865–2873
Representative UV–Vis spectra of [(L1sal)Ru(CO)(Cl)(PPh3)], [(L1
Ru] and [(L1nap)Ru(CO)(Cl)(PPh3)] have been given in Fig. 1.
Complex [(OL)Ru(PPh3)Cl] displayed low energy absorption at
1040 nm. The spectra of ligand HL and Complex [(OL)Ru(PPh3)Cl]
are shown in Fig. 2.
Relevant UV–Vis spectral data are collected in experimental
section and the spectra of other the new compounds are given in
Figs. S1–S14 as Supplementary materials.
)
(–N@CH–) nitrogen [12]. The mNH of ligand HL appeared at
3401 cmꢀ1 and mC@N is absent indicating reduction of C@N to the
dihydro species. Whereas, the IR band at 1600 cmꢀ1 and no trace
of mNH for [(OL)Ru(PPh3)Cl] signified the conversion of reduced
imine of HL into imine form during the complexation. The mN@N
of [(Lsal)Ru(CO)(Cl)(PPh3)], [(Lnap)Ru(CO)(Cl)(PPh3)], [(Lsal)2Ru] and
[(OL)Ru(PPh3)Cl] appeared at slightly lower frequency range
sal 2-
(1425–1435 cmꢀ1) than those of the ligands (1450–1483 cmꢀ1
)
IR spectra of all the complexes were recorded in solid KBr sup-
port. The [(Lsal)Ru(CO)(Cl)(PPh3)], [(Lnap)Ru(CO)(Cl)(PPh3)] and
[(Lsal)2Ru] complexes exhibited mC@N absorptions (ꢁ1607, 1615
and 1603 cmꢀ1, respectively) at slightly lower frequency than that
of the corresponding ligands HLsal and HLnap (ꢁ1615 and
ꢁ1624 cmꢀ1, respectively) indicating coordination of aldimine
indicating coordination of azo (–N@N–) nitrogen [13]. A sharp sin-
glet near 1940 cmꢀ1 has been assigned to mC@O for [(Lsal)Ru
(CO)(Cl)(PPh3)] and [(Lnap)Ru(CO)(Cl)(PPh3)] [13]. Relevant IR spec-
tral data are collected in experimental section and the spectra of all
the new compounds are given in Figs. S15–S28 in Supplementary
material.
The composition of [(Lsal)Ru(CO)(Cl)(PPh3)], [(Lsal)2Ru] and [(Lna-
p)Ru(CO)(Cl)(PPh3)] matched well with the C, H, N analytical data
and 1H NMR spectral data. The 1H NMR spectra of the complexes
Fig. 3. Molecular structure of [(L1sal)Ru(CO)(Cl)(PPh3)] with atom numbering
scheme. The hydrogen atoms excepting on –N@C–H (13) of the imine group has
been omitted for clarity.
Fig. 5. Molecular structure of [(L1nap)Ru(CO)(Cl)(PPh3)] with atom numbering
scheme. The hydrogen atoms excepting on –N@C–H (13) of the imine group has
been omitted for clarity.
Fig. 4. Molecular structure of [(L1sal)2Ru] with atom numbering scheme. The
hydrogen atoms excepting on –N@C–H (13, 32) of the imine groups have been
omitted for clarity.
Fig. 6. Molecular structure of [(OL)Ru(PPh3)Cl] with atom numbering scheme. The
hydrogen atoms excepting on –N@C–H (13) of the imine group has been omitted for
clarity.

P. Pattanayak et al. / Inorganica Chimica Acta 363 (2010) 2865–2873
2869
Table 1
2.3. X-ray structure
Selected bond distances (Å) and angles (°) for [(L1sal)Ru(CO)(PPh3)(Cl)], [(L1sal)2Ru],
[(L1nap)Ru(CO)(Cl)(PPh3)] and [(OL)Ru(PPh3)Cl].
Crystal structures of [(L1sal)Ru(CO)(Cl)(PPh3)], [(L1sal)2Ru], [(L1
p)Ru(CO)(Cl)(PPh3)] and [(OL)Ru(PPh3)Cl] were determined by sin-
na-
[(L1sal)Ru(CO)(PPh3)(Cl)]
Ru–Cl
Ru–P
Ru–O1
Ru–N1
Ru–C38
O1–Ru–N1
Cl–Ru–O1
O1–Ru–N3
Ru–O1–C19
N1–Ru–N3
Ru–N3–C12
2.414 (2)
2.345 (1)
2.103 (4)
2.162 (1)
1.838(2)
91.63(6)
89.12(4)
84.57(6)
123.42(12)
80.87(7)
116.19(12)
Ru–N3
N3–C13
N1–N2
O1–C19
2.055 (2)
1.298(3)
1.266(2)
1.310(2)
gle crystal X-ray crystallography. The perspective views of the
molecular structures of [(L1sal)Ru(CO)(Cl)(PPh3)], [(L1sal)2Ru], [(L1
na-
p)Ru(CO)(Cl)(PPh3)] and [(OL)Ru(PPh3)Cl] are given in Figs. 3–6,
respectively with atom numbering scheme. Selected bond dis-
tances and angles are given in Table 1.
Tridentate N,N,O donor Lsal and Lnap are bound facially to the
Ru(II) centre in [(L1sal)Ru(CO)(Cl)(PPh3)] and [(L1nap)Ru(CO)(Cl)(PPh3)]
along with three monodentate ligands Clꢀ, CO and PPh3 in a distorted
P–Ru–N3
97.74(5)
N1–C1–C2
Ru–N3–C13
Ru–N1–N2
N1–N2–C7
118.43(18)
126.73(14)
124.53(14)
120.69(17)
ꢀ
ꢀ
ꢀ
octahedral geometry. Two N,N,O donor Lsal ligands are coordinated
meridionally in [(L1sal)2Ru] complex and the geometry about Ru(II) is
distorted octahedral. Octahedral ruthenium centre of [(OL)Ru(PPh3)Cl]
is equatorially coordinated by tetradentate (O,N,N,O) dianionic (OL)2ꢀ
ligand. Chloride (Clꢀ) and phosphine (PPh3) ligands are held at axial
trans positions. The Ru–N(azo), Ru–N(imine) and Ru–O distances in
[(L1sal)2Ru] (av. 1.978, 2.047 and 2.037 Å, respectively) are shorter than
those of [(L1sal)Ru(CO)(Cl)(PPh3)] (2.162(1), 2.055(2) and 2.103(1) Å).
The Ru–N(azo), Ru–N(imine) and Ru–O lengths of [(L1nap)Ru
(CO)(Cl)(PPh3)] are marginally shorter than [(L1sal)Ru(CO)(Cl)(PPh3)]
which is attributed to enhanced conjugation due to the napthyl ring.
In general, Ru–N and Ru–O distances are shorter in [(OL)Ru(PPh3)Cl]
than the other three complexes in concurrence with higher oxidation
state of Ru (i.e. Ru(III)) in [(OL)Ru(PPh3)Cl]. The molecular structure of
[(OL)Ru(PPh3)Cl] confirmed the oxygenation of the phenyl ring (C14–
C19). The N3–C13 distances in all the complexes are within the range
1.298(3)–1.318(2) Å which is similar to N-coordinated aldimine C–N
distances [12,14,15]. Azo (N@N) distances in all the complexes are
within the normal range (1.266(3)–ꢀ1.291(2) Åꢀ) [14]. The azo (N@N)
distances in facially coordinated Lsal and ꢀLnap ligands (av. 1.266 Å)
are shorter than meridionally bound Lsal and coordinated (OL)2ꢀ
[(L1sal)2Ru]
Ru–O1
Ru–O2
Ru–N1
Ru–N3
2.039 (1)
2.036 (1)
1.977 (2)
2.045 (2)
1.979 (1)
1.313(1)
86.80(5)
175.38(6)
93.40(6)
89.88(6)
132.05(15)
90.96(7)
94.04(7)
125.21(12)
Ru–N5
Ru–N6
N4–N5
N2–N1
N6–C32
O1–C19
O1–Ru–N6
O2–Ru–N1
O2–Ru–N3
O2–Ru–N4
O2–Ru–N6
N1–Ru–N4
N3–Ru–N4
N4–Ru–N6
1.979 (1)
2.049 (1)
1.280(2)
1.269(2)
1.318(2)
1.301(2)
81.50(6)
92.29(6)
82.23(6)
174.01(6)
93.36(6)
91.41(7)
93.01(6)
91.07(6)
Ru–N4
N3–C13
O1–Ru–O2
O1–Ru–N1
O1–Ru–N3
O1–Ru–N4
Ru–N1–N2
N1–Ru–N3
N1–Ru–N6
Ru–O1–C19
[(L1nap)Ru(CO)(Cl)(PPh3)]
Ru–Cl
Ru–P
Ru–O1
Ru–N1
Ru–N3
O1–Ru–N1
P–Ru–N3
Cl–Ru–O1
Ru–O1–C19
Cl–Ru–N1
Cl–Ru–N3
2.406 (1)
O1–C19
N3–C13
N1–N2
Ru–C24
1.298 (9)
1.311(2)
1.266 (1)
1.835 (1)
2.338 (1)
2.096 (1)
2.160 (1)
2.048 (2)
91.63(6)
96.02(3)
89.29(3)
127.56(9)
91.50(3)
170.86(3)
O1–Ru–N3
Ru–N3–C13
Ru–N3–C12
N1–Ru–N3
Ru–N1–N2
84.57(6)
126.73(14)
116.19(12)
80.87(7)
ligands (av. 1.280 Å) signifying superior metal to azo (N@N)
p back
bonding in [(L1sal)2Ru] and [(OL)Ru(PPh3)Cl].
125.12(9)
[(OL)Ru(PPh3)Cl]
Ru–Cl
Ru–P
Ru–O1
Ru–O2
2.434 (2)
2.361 (1)
2.032 (1)
1.998 (1)
1.957 (2)
173.80(5)
179.07(2)
85.03(4)
90.68(4)
90.42(4)
90.48(4)
93.29(5)
O1–C15
O2–C2
N1–N2
Ru–N3
1.312(2)
1.311(2)
1.291(2)
2.000 (1)
1.300(2)
3. Conclusions
Reactions of several tridentate (N,N,O) donor azo ligands with
Ru(II) substrates have been carried out to prepare new Ru(II) and
Ru(III) complex. The results have been summarised and shown
schematically in Scheme 2 with the reaction conditions.
The Ru(II) substrate, Ru(H)(CO)(Cl)(PPh3)3, underwent ligand
substitution with one Lsalꢀ or Lnapꢀ to form [(Lsal)Ru(CO)(Cl)(PPh3)]
or [(Lnap)Ru(CO)(Cl)(PPh3)], respectively. In both the complexes tri-
dentate (N,N,O) donor ligands coordinated the metal centre
facially.
Ru–N2
N3–C13
O2–Ru–N3
Cl–Ru–P
Cl–Ru–N2
Cl–Ru–N3
P–Ru–O1
P–Ru–O2
O1–Ru–O2
N2–Ru–N3
Ru–N2–N1
Ru–N2–C7
Ru–N3–C12
Ru–O2–C2
Ru–O1–C15
O1–Ru–N2
82.59(6)
129.48(12)
113.67(11)
112.43(10)
121.47(11)
124.55(11)
172.18(5)
In the case of [(Lsal)Ru(CO)(Cl)(PPh3)], further substitution oc-
curred in presence of excess HLsal ligand to form (Lsal)2Ru where
the ligands are meridionally coordinated. Preparation of [(Lsal)2Ru]
upon treatment of [(Lsal)Ru(CO)(Cl)(PPh3)] with HLsal indicated
stepwise formation of [(Lsal)2Ru] in conjunction with geometrical
isomerisation of the ligand coordination. On contrary to this,
[(Lnap)2Ru] complex was not obtained in presence of excess ligand
or upon treatment of [(Lnap)Ru(CO)(Cl)(PPh3)] with HLnap. There-
fore, HLnap dictated the formation of [(Lnap)Ru(CO)(Cl)(PPh3)]
exclusively. The new ligand HL was synthesized by reducing the
were recorded in CDCl3. The Phenolic OH signal of HLsal (ꢁd 13.60)
and HLnap (ꢁd 13.15) ligands were absent in the spectra of these
complexes indicating the coordination of phenoxide O. The aldim-
ine (–CH@N–) proton resonance of [(Lsal)Ru(CO)(Cl)(PPh3)] (ꢁd
8.5), and [(Lsal)2Ru] (ꢁd 8.67) shifted marginally compared to the
HLsal ligand (ꢁd 8.63). The aldimine (–CH@N–) proton resonance
of HLnap appeared as doublet near d 9.20 due to the protonation
of imine nitrogen by the phenolic proton via intramolecular hydro-
gen bonding. The ligand HL displayed well resolved spectrum
where methylene proton resonances appeared at d 4.29. OH and
NH proton resonances appeared at d 8.11 and d 6.72, respectively.
The aromatic protons of all the compounds appeared in the range d
6.87–d 7.95. Relevant NMR spectral data are collected in experi-
mental section and the spectra are given in Figs. S29–S41 as Sup-
plementary material.
aldimine function of HL1 with the expectation to obtain more
sal
flexible ligand. Reaction of HL with Ru(PPh3)3Cl2 in aerobic condi-
tion produced the new complex [(OL)Ru(PPh3)Cl] after oxygena-
tion at the ortho position of pendent phenyl ring. Oxidation of
dihydro aldimine to aldimine and Ru(II) to Ru(III) were occurred
during the reaction. Mechanism of this aromatic oxygenation is un-
clear at present and it is supposed that metal and ligand oxidations
prior to oxygenation produced reactive oxygen species (ROS) by

2870
P. Pattanayak et al. / Inorganica Chimica Acta 363 (2010) 2865–2873
HLsal
HLnap
*
[(Lsal)Ru(CO)(Cl)(PPh3)]
[(Lnap)Ru(CO)(Cl)(PPh3)]
(i)
(ii)
HLsal
HLnap
+
HLsal
HLnap
[(Lsal)2Ru]
Ru(H)(CO)(Cl)(PPh3)3
[(Lnap)2Ru]
+
(iii)
(iv)
Ru(PPh3)3Cl2
HL
NaBH4
HL1
sal
[(OL)Ru(PPh3)Cl]
(i) 1:1 stoichiometric ratio with respect to HLsal and Ru(H)(CO)(Cl)(PPh3)3, 8h refluxin toluene
(ii) 1:1 stoichiometric ratio with respect to HLnap and Ru(H)(CO)(Cl)(PPh3)3, 8h refluxin toluene
(iii)
(iv)
Excess HLsalwith respect to Ru(H)(CO)(Cl)(PPh3)3, ~ 24h reflux in toluene
Excess HLnapwith respect to Ru(H)(CO)(Cl)(PPh3)3, ~ 24h reflux in toluene
*This is major product with a minor amount of [(Lsal)2Ru]
Scheme 2.
reducing the dioxygen. The ROS, thus produced, oxygenated the
phenyl ring via metal mediated pathway.
(d, 1H, Ph); 7.74 (d, 1H, Ph); 7.62 (d, 2H, Ph); 7.58–7.54 (m, 3H,
Ph); 7.51–7.44 (m, 2H, Ph); 7.36–7.25 (m, 2H, Ph).
4.2.1.2. HL2
2b. Yield: 0.14 g (85%). Anal. Calc. for HL2nap: C,
nap
4. Experimental
78.88; H, 5.24; N, 11.49. Found: C, 78.85; H, 5.26; N, 11.52%. Elec-
tronic spectrum (kmax/nm (
/dm2 molꢀ1), dichloromethane): 358
(8662); 319 (12 039); 231 (30 318). IR (KBr pellets, cmꢀ1):
(N@N) 1483;
(C@N) 1620. 1H NMR (CDCl3, ppm): d 13.15 (s,
e
4.1. Materials
m
m
All commercially available chemicals and solvents utilized dur-
ing the present work were of analytical grade and in most of the
cases these were used as obtained. The chemicals and there sources
were as follows: Salicylaldehyde, benzene, dichloromethane, aceto-
nitrile, petroleum ether, sodium hydroxide, diethyl ether, formalde-
hyde, triphenylphosphene, methylcellosolve, Sodium borohydride
from E. Merck (India). Ruthenium chloride was purchased from
Johnson Mathey. 2-Hydroxy-1-naphthaldehyde was prepared
according to a reported procedure [16]. Ru(H)(CO)(Cl)(PPh3)3,
Ru(PPh3)3Cl2 were prepared following a procedure reported earlier
[17]. All the solvents were purified and distilled after receiving from
E. Merck India. Silical gel G with binder was used for thin layer
chromatography.
1H, OH); 10.81 (s,1H, –CH@N); 9.17 (d, 1H, Ph); 9.18 (d, 1H, Ph);
8.05 (d, 1H, Ph); 7.95 (d, 1H, Ph); 7.85 (d, 1H, Ph); 7.70 (d, 1H,
Ph); 7.58 (t, 2H, Ph); 7.51 (t, 1H, Ph); 7.44 (t, 1H, Ph); 7.35 (d,
2H, Ph); 7.29–7.26 (m, 2H, Ph); 6.95 (d, 1H, Ph); 2.43 (s, 3H).
4.2.1.3. HL3
2c. Yield: 0.13 g (80%). Anal. Calc. for HL3nap: C,
nap
71.59; H, 4.17; N, 10.89. Found: C, 71.62; H, 4.20; N, 10.92%. Elec-
tronic spectrum (kmax/nm (
/dm2 molꢀ1), dichloromethane): 335
(15 860); 314 (18 215); 235 (42 439). IR (KBr pellets, cmꢀ1):
(N@N) 1482;
(C@N) 1615. 1H NMR (CDCl3, ppm): d 13.15 (s,1H,
e
m
m
OH); 10.83 (s,1H, –CH@N); 9.20 (d, 1H, Ph); 9.19 (d,1H, Ph); 8.12
(d, 1H, Ph); 7.99 (d, 2H, Ph); 7.89 (d, 1H, Ph); 7.81–7.76 (m, 1H,
Ph); 7.73(d, 1H, Ph); 7.62 (d, 1H, Ph); 7.60–7.56 (m, 1H, Ph); 7.54
(d, 1H, Ph); 7.49–7.42 (m, 1H, Ph); 7.32–7.28 (m, 1H, Ph); 7.20 (t,
1H, Ph); 6.96 (d, 1H, Ph).
4.2. Syntheses of compounds
4.2.1. Preparation of ligands
The 1-{[2-(arylazo)phenyl]iminomethyl}-2-phenol ligands,
HLsal, were synthesized by the reported procedure [12]. 1-{[2-(ary-
lazo)phenyl]iminomethyl}-2-napthol, HLnap ligands were prepared
4.2.1.4. HL 3. To a 40 mL methanolic solution of 1-{[2-(pheny-
lazo)phenyl]iminomethyl}-2-phenol, HL1sal, (0.5 g, 1.66 mmol) lit-
tle excess of NaBH4 (0.065 g, 1.7 mmol) was added. The resulting
mixture was then stirred for 1 h. The solvent was then evaporated.
The resulting solid mass was washed with water and the mass was
extracted with dichloromethane. After evaporation of the solvent
the ligand was introduced for purification by thin layer chromatog-
raphy on silica gel using pet ether: toluene (50:50 V/V). The lower
band was collected as pure compound. Isolated yield: 0.478 g
(95%). Anal. Calc. for C19H17N3O: C, 75.24; H, 5.61; N, 13.86. Found:
C, 75.27; H, 5.62; N, 13.88%. Electronic spectrum (kmax/nm
by the following procedure as described below for HL1
.
nap
4.2.1.1. HL1nap 2a. 2-(Phenylazo) aniline (0.1 g, 0.50 mmol) was dis-
solved in dry diethyl ether (40 mL), and to it 2-hydroxy-1-naph-
thaldehyde (0.087 g, 0.50 mmol) was added. The mixture was
then refluxed for 9 h and solvent was evaporated in vaccuo for
2 h to obtain the solid product. It was further kept in a vacuum des-
iccator for 24 h before use and characterization. Yield: 0.16 g (90%).
Anal. Calc. for HL1nap: C, 78.61; H, 4.87; N, 11.95. Found: C, 78.63; H,
4.90; N, 11.97%. Electronic spectrum (kmax/nm (
dichloromethane): 334 (12 096), 311 (14 073), 235 (39 384). IR
(KBr pellets, cmꢀ1): (C@N) 1624. 1H NMR (CDCl3,
(N@N) 1481;
e
/dm2 molꢀ1),
(e
/dm2 molꢀ1), dichloromethane): 435 (3240), 319 (7000), 239
(7440). IR (KBr pellets, (–NH) 3182;
, cmꢀ1): (N@N) 1454. 1H
m
m
m
m
m
NMR (CDCl3, ppm): d 8.11 (s, NH); 7.83–7.85 (d, 1H, Ph); 7.76–
7.79 (m, 2H, Ph); 7.45–7.49 (m, 2H, Ph); 7.39–7.42 (m, 1H, Ph);
7.20–7.26 (m, 2H, Ph); 6.87–6.96 (m, 3H, Ph); 4.29 (d, CH2).
ppm): d 13.17 (s, 1H, OH); 10.82 (s, 1H, –CH@N); 9.22 (d, 1H,
Ph); 9.21 (d, 1H, Ph); 8.18–8.15 (m, 2H, Ph); 7.98 (d, 1H, v); 7.90

P. Pattanayak et al. / Inorganica Chimica Acta 363 (2010) 2865–2873
2871
4.2.2. Synthesis of complexes
7.48 (m, 1H, Ph); 7.42–7.38 (m, 1H, Ph); 7.16 (t, 1H, Ph); 6.78–
6.71 (m, 4H, Ph); 6.46 (d, 1H, Ph); 6.24 (d, 2H, Ph).
4.2.2.1. [(L1sal)Ru(CO)(Cl)(PPh3)] and [(L1sal)2Ru] 4a and 5a. 1-{[2-
(Phenylazo)phenyl]iminomethyl}-2-phenol, (0.063 g, 0.209 mmol)
was dissolved in 40 mL toluene and to it Ru(H)(CO)(Cl)(PPh3)3
(0.1 g, 0.105 mmol) was added. The mixture was then heated to re-
flux for 8 h to afford greenish brown solution. Evaporation of the
solvent gave a greenish brown residue, which was introduced for
purification by thin layer chromatography on silica gel. Two green
bands separated in toluene–acetonitrile (95:5, V/V) mixed solvent.
From the first and second bands [(L1sal)Ru(CO)(Cl)(PPh3)] and
[(L1sal)2Ru], respectively, were isolated in pure form upon extract-
ing with dichloromethane and methanol.
4.2.2.4. [(L1nap)Ru(CO)(Cl)(PPh3)] 6a. 1-{[2-(Phenylazo)phenyl]imi-
nomethyl}-2-napthol, HL1
(0.2 g, 0.57 mmol) was dissolved in
nap
50 mL toluene and to it Ru(H)(CO)(Cl)(PPh3)3 (0.27 g, 0.28 mmol)
was added. The mixture was then heated to reflux for 5 h to afford
the greenish brown solution. Evaporation of the solvent gave a
greenish brown residue which was introduced for purification by
thin layer chromatography on silica gel. Green band separated in
benzene–acetinitrile (95:5) mixed solvent and was isolated in pure
form upon extracting with dichloromethane and methanol. Yield:
0.132 g (60%). Anal. Calc. for complex [(L1nap)Ru(CO)(Cl)(PPh3)]: C,
64.85; H, 3.98; N, 5.40. Found: C, 64.83; H, 4.00 N, 5.42%. Electronic
[(L1sal)Ru(CO)(Cl)(PPh3)]: Yield: 0.045 g (60%). Anal. Calc. for
[(L1sal)Ru(CO)(Cl)(PPh3)]: C, 62.71; H, 3.98; N, 5.77. Found: C,
62.68; H, 4.00; N, 5.80%. Electronic spectrum (kmax/nm
dm2 molꢀ1), dichloromethane): 437 (4500); 341 (17 968); 232
(52 395). IR (KBr pellets, cmꢀ1):
(N@N) 1436; (C@N) 1607;
(CO) 1941. 1H NMR (CDCl3, ppm): d 8.51 (d,1H, Ph); 7.94–7.92
(
e
/
spectrum (kmax/nm (
450 (5600), 340 (19 600). IR (KBr pellets, cmꢀ1):
(C@N) 1613,
(CO) 1945. 1H NMR (CDCl3, ppm): d 8.43 (d, 2H,
e
/dm2 molꢀ1), dichloromethane): 600 (1250),
(N@N) 1433,
m
m
m
m
m
m
Ph); 7.93 (t, 1H, Ph); 7.77–7.64 (m, 6H, PPh3); 7.52 (t, 2H, Ph);
7.46 (t, 3H, PPh3); 7.28–7.24 (m, 3H, PPh3); 7.19 (t, 4H, PPh3);
7.12 (t, 1H, Ph); 7.06 (d, 1H, Ph); 7.00 (d, 1H, Ph); 6.49 (t, 1H, Ph).
(m,1H, Ph); 7.67 (t, 6H, Ph); 7.51 (t, 2H, Ph); 7.47–7.45 (m, 3H,
PPh3); 7.34 (t, 3H, PPh3); 7.29–7.25 (m, 9H, PPh3); 7.05 (t, 2H,
Ph); 6.85 (d, 1H, Ph); 6.62 (t, 1H, Ph); 6.38 (d,1H, Ph); 6.24 (t, 1H,
Ph).
4.2.2.5. [(L2nap)Ru(CO)(Cl)(PPh3)] 6b. The complexes [(L2nap)Ru
(CO)(Cl)(PPh3)] was prepared following the same procedure as in
the cases of [(L1nap)Ru(CO)(Cl)(PPh3)] using HL2nap, in place of
HL1nap. The solvent used for thin layer chromatographic separation
is toluene–acetonitrile (95:5 V/V) mixed solvent. Yield: 0.128 g
(57%). Anal. Calc. for complex [(L2nap)Ru (CO)(Cl)(PPh3)]: C, 65.21;
H, 4.58; N, 5.30. Found: C, 65.19; H, 4.60; N, 5.27%. Electronic spec-
[(L1sal)2Ru]: Yield: 0.018 g (25%). Anal. Calc. for [(HL1sal)2Ru]: C,
53.99; H, 3.97; N, 11.97. Found: C, 60.01; H, 3.95; N, 11.95%. Elec-
tronic spectrum (kmax/nm (
(6500); 508 (3320); 403 (8340); 357 (11 960). IR (KBr pellets,
cmꢀ1): (C@N) 1604. 1H NMR (CDCl3, ppm): d 8.67
(N@N) 1454,
e
/dm2 molꢀ1), dichloromethane): 625
m
m
(s, 1H, –CH@N); 7.96 (dd, 1H, Ph); 7.52 (d, 1H, Ph); 7.46 (t, 1H,
Ph); 7.27–7.24 (m, 1H, Ph); 7.16–7.12 (m,1H, Ph); 6.94 (t, 1H,
Ph); 6.79 (t, 2H, Ph); 6.72–6.66 (m, 2H, Ph); 6.48 (d, 1H, Ph);
6.31(d, 2H, Ph).
trum (kmax/nm (
(5563); 360 (19 300). IR (KBr pellets, cmꢀ1):
(C@N) 1616,
(CO) 1955. 1H NMR (CDCl3, ppm): d 8.38 (d, 2H,
e
/dm2 molꢀ1), dichloromethane): 600 (940); 450
(N@N) 1435,
m
m
m
Ph); 7.90 (t, 1H, Ph); 7.77–7.64 (m, 6H, PPh3); 7.50–740 (m, 4H,
PPh3); 7.33–7.25 (m, 4H, PPh3); 7.19 (t, 5H, PPh3); 7.14 (t, 1H,
Ph); 7.03 (d, 1H, Ph); 7.00 (d, 1H, Ph); 6.48 (d, 1H, Ph); 2.42 (s, CH3).
4.2.2.2. [(L2sal)Ru(CO)(Cl)(PPh3)] and [(L2sal)2Ru] 4b and 5b. [(L2sal)-
Ru(CO)(Cl)(PPh3)]: Yield: 0.042 g (55%). Anal. Calc. for Complex
[(L2sal)Ru(CO)(Cl)(PPh3)]: C, 63.14; H, 4.04; N, 5.66. Found: C, 63.10;
H, 4.00; N, 5.70%. Electronic spectrum (kmax/nm (
dichloromethane): 441 (6250); 355 (15 524); 232 (59 531). IR (KBr
pellets, cmꢀ1): (CO) 1949. 1H NMR
(N@N) 1435, (C@N) 1605,
e
/dm2 molꢀ1),
4.2.2.6. [(L3nap)Ru(CO)(Cl)(PPh3)] 6c. The complexes [(L3nap)Ru
(CO)(Cl)(PPh3)] was prepared following the same procedure as in
the cases of [(L1nap)Ru(CO)(Cl)(PPh3)] using HL3nap, in place of
HL1nap. The solvent used for thin layer chromatographic separation
is toluene–acetonitrile (95:5 V/V) mixed solvent. Yield: 0.119 g
(52%). Anal. Calc. for complex [(L1nap)Ru(CO)(Cl)(PPh3)]: C, 62.09;
H, 3.69; N, 5.17. Found: C, 62.10; H, 3.67; N, 5.20%. Electronic spec-
m
m
m
(CDCl3, ppm): d 8.45 (d, 1H, Ph); 7.91–7.89 (m, 1H, Ph); 7.69 (t, 6H,
PPh3); 7.46–7.43 (m, 2H, PPh3); 7.34–7.25 (m, 7H, PPh3); 7.06–7.03
(m, 1H, Ph); 6.82 (d, 1H, Ph); 6.62–6.60 (m, 1H, Ph); 6.38 (d, 1H, Ph);
6.23 (t, 1H, Ph).
[(L2sal)2Ru]: Yield: 0.0087 g (12%). Anal. Calc. for [(L2sal)2Ru]: C,
65.77; H, 4.38; N, 11.51. Found: C, 65.74; H, 4.40; N, 11.49%. Elec-
trum (kmax/nm (
(5072), 350 (18 555). IR (KBr pellets, cmꢀ1):
(C@N) 1614,
(CO) 1959. 1H NMR (CDCl3, ppm): d 8.46 (d, 2H,
e
/dm2 molꢀ1), dichloromethane): 600 (690), 450
(N@N) 1435,
m
tronic spectrum (kmax/nm (
(7336), 507 (4750), 404 (10 828), 354 (16 038). IR (KBr pellets,
cmꢀ1): (C@N) 1602. 1H NMR (CDCl3, ppm): d 8.67
(N@N) 1454,
e
/dm2 molꢀ1), dichloromethane): 626
m
m
Ph); 7.91 (t, 1H, Ph); 7.69–7.63 (m, 6H, PPh3); 7.28–7.24 (m, 3H,
PPh3); 7.22–7.18 (m, 4H, PPh3); 7.13 (t, 1H, Ph); 7.03 (d, 1H, Ph);
6.98 (d, 1H, Ph); 6.50 (t, 1H, Ph).
m
m
(s, 1H, –CH@N); 7.95 (dd, 1H, Ph); 7.52 (d, 1H, Ph); 7.45–7.42 (m,
1H, Ph); 7.27–7.24 (m, 1H, Ph); 7.14–7.11 (m, 1H, Ph); 6.71–6.67
(m, 2H, Ph); 6.56 (d, 2H, Ph); 6.47 (d, 1H, Ph); 6.21(d, 2H, Ph).
4.2.2.7. [(OL)Ru(PPh3)Cl] 7. Ligand HL (63 mg, 0.209 mmol) was dis-
solved in 40 mL toluene and to it Ru (PPh3)3Cl2 (100 mg,
0.105 mmol) was added. The mixture was then heated to reflux
for 8 h to afford brown solution. Evaporation of the solvent affor-
ded brown crystals of composition [(OL)Ru(PPh3)Cl]. The [(OL)-
Ru(PPh3)Cl] was synthesized by the same procedure as described
above using authentic ligand H2OL in place of ligand HL. Yield:
0.037 g (50%). Anal. Calc. for [(OL)Ru(PPh3)Cl]: C, 63.14; H, 4.04;
N, 5.66. Found: C, 63.10; H, 4.00; N, 5.70%. Electronic spectrum
4.2.2.3. [(L3sal)Ru(CO)(Cl)(PPh3)] and[ (L3sal)2Ru] 4c and 5c. [(L3sal)-
Ru(CO)(Cl)(PPh3)]: Yield: 0.044 g (55%). Anal. Calc. for complex
[(L3sal)Ru(CO)(Cl)(PPh3]): C, 59.87; H, 3.67; N, 5.51. Found: C, 59.90;
H, 3.65; N, 5.55%. Electronic spectrum (kmax/nm (
dichloromethane): 437 (4150); 351 (15 524); 232 (45 781). IR (KBr
pellets, cmꢀ1): (CO) 1949. 1H NMR
(N@N) 1434; (C@N) 1605;
e
/dm2 molꢀ1),
m
m
m
(CDCl3, ppm): d 8.55 (d, 1H, Ph); 7.94–7.91 (m, 2H, Ph); 7.64 (t, 6H,
PPh3); 7.49 (t, 5H, PPh3); 7.35–7.26 (m, 8H, PPh3); 7.07 (t, 2H, Ph);
6.83 (d,1H, Ph); 6.64 (t, 1H, Ph); 6.38 (d, 1H, Ph); 6.26 (t,1H, Ph).
(kmax/nm
(1560), 464 (10 360), 339 (14 000), 303 (13 440). IR (KBr pellets,
cmꢀ1):
(NH) 3042, (C@N) 1600, (N@N) 1434, (Ru–Cl) 295.
(e
/dm2 molꢀ1), dichloromethane): 1043 (1823), 639
[(L3sal)2Ru]: Yield: 0.011 g (14%). Anal. Calc. for complex [(L3
)
m
m
m
m
sal 2-
Ru]: C, 59.16; H, 3.37; N, 10.89%. Found: C, 59.20; H, 3.40; N,
10.85%. Electronic spectrum (kmax/nm (
/dm2 molꢀ1), dichloro-
methane): 632 (6918), 511 (5110), 401 (10 175), 358 (14 660). IR
(KBr, cmꢀ1): (C@N) 1603. 1H NMR (CDCl3, ppm):
(N@N) 1455,
d 8.68 (s, 1H, –CH@N); 7.96 (dd, 1H, Ph); 7.54–7.50 (m, 1H, Ph);
e
4.3. Physical measurements
m
m
Microanalysis (C, H, N) was performed using a Perkin–Elmer
2400 C, H, N, S/O series II elemental analyzer. Infrared spectra were

2872
P. Pattanayak et al. / Inorganica Chimica Acta 363 (2010) 2865–2873
Table 2
Crystallographic data for [(L1sal)Ru(CO)(Cl)(PPh3)], [(L1sal)2Ru], [(L1nap)Ru(CO)(Cl)(PPh3)] and [(OL)Ru(PPh3)Cl].
[(L1sal)Ru(CO)(Cl)(PPh3)]
[(L1sal)2Ru]
[(L1nap)Ru(CO)(Cl)(PPh3)]
[(OL)Ru(PPh3)Cl]
Chemical formula
Formula weight
Crystal system
Space group
a (Å)
C38H29ClN3O2PRu
727.13
monoclinic
P21/n
11.1840(1)
20.0490(2)
14.5660(2)
90
100.6800
90
0.71073
3209.53(6)
1480
C38H28N6O2Ru
701.73
C42H31ClN3O2PRu
777.19
monoclinic
P21/n
9.3910(4)
20.7543(8)
17.8198(6)
90
97.378(2)
90
0.71073
3444.4(2)
1584
C37H28ClN3O2PRu
714.11
triclinic
triclinic
ꢀ
ꢀ
P1
P1
9.7770(1)
10.8280(2)
15.8320(3)
71.6890(10)
74.1380(10)
84.4700(10)
0.71073
1530.50(4)
716
10.2515(2)
11.0396(2)
15.0526(2)
77.2190(10)
77.6140(10)
70.5910(10)
0.71073
1548.40(5)
726
b (Å)
c (Å)
a
(°)
b (°)
(°)
c
k (Å)
V (Å3)
F(0 0 0)
Z
4
2
4
2
T (K)
150
1.505
0.661
150
1.523
0.559
293
1.499
0.622
293
1.532
0.684
D (g cmꢀ3
)
l
(mmꢀ1
)
R1 (all data)
wR2 [I > 2r(I)]
GOF
0.0324
0.0863
1.01
0.0285
0.0680
1.07
0.0220
0.0599
0.99
0.0247
0.0635
1.08
h minimum, maximum (°)
3.8, 30.0
0.047
9362
3.8, 27.5
0.035
6979
1.5, 28.7
0.023
8894
1.4, 28.7
0.024
8008
Rint
Nref
Npar
415
425
451
406
recorded on a Parkin–Elmer L120-00A FT-IR spectrometer with the
samples prepared as KBr pellets. Electronic spectra were recorded
on a Shimadzu UV-1601 PC spectrophotometer. 1H NMR spectra
were obtained on Brucker DPX 400 and Brucker 500 RPX NMR
spectrometers in CDCl3 using TMS as the internal standard.
plementarydata associated with thisarticlecan be found, inthe online
version, at doi:10.1016/j.ica.2010.04.016.
References
[1] (a) H. Adams, R.M. Bucknal, D.E. Fenton, M. Graccia, J. Oakes, Polyhedron 17
(1998) 4169;
(b) S. Mukhopadhyay, D. Ray, Dalton Trans. (1995) 265.
[2] S. Basu, S. Halder, I. Pal, S. Samanta, P. Karmakar, M.G.B. Drew, S. Bhattacharya,
Polyhedron 27 (2008) 2943.
[3] (a) P. Chaudhuri, K. Wieghardt, Prog. Inorg. Chem. 35 (1987) 329;
(b) A.J. Blake, M. Schröder, Adv. Inorg. Chem. 35 (1990) 1;
(c) B.R. Cameron, M.C. Darkes, I.R. Baird, R.T. Skerlj, Z.L. Santucci, S.P. Fricker,
Inorg. Chem. 42 (2003) 13.
4.4. Crystallography
Crystals of [(L1sal)Ru(CO)(Cl)(PPh3)], [(L1sal)2Ru], [(L1nap)Ru
(CO)(Cl)(PPh3)] and [(OL)Ru(PPh3)Cl] were grown by slow evapora-
tion of dicholoromethane–acetonitrile mixed solution at 298 K.
Data were collected on a Brucker SMART CCD diffractometer using
[4] (a) M.R.St.-J. Foreman, A.F. Hill, G.R. Owen, A.J.P. White, D.J. Williams,
Organometallics 22 (2003) 4446;
Mo Ka monochromator (k = 0.71073). Structure solutions were
(b) A.N.W. Cannadine, J.C. Clark, G.R. Hill, J. Chem. Soc., Dalton Trans. (1993)
1131;
(c) A. Hill, F. Alcock, N.W. Cannadine, J.C. Clark, G.R. Owen, J. Organomet. Chem.
426 (1992) C40;
(d) J.C. Cannadine, A.F. Hill, A.J.P. White, D.J. Williams, J.D.E.T. Wilton-Ely,
Organometallics 15 (1996) 5409;
performed using SHELX-97 PC version program [18]. All the non-
hydrogen atoms were refined anisotropically using full-matrix
least squares method. Hydrogen atoms were included for structure
factor calculations after placing them at calculated positions. The
data collection parameters and relevant crystal data are collected
in Table 2.
(e) X. Sala, I. Romero, M. Rodríguez, A. Llobet, Inorg. Chem. 43 (2004) 5403.
[5] (a) S. Trofimenko, Chem. Rev. 93 (1993) 943;
(b) S. Trofimenko, J. Am. Chem. Soc. 88 (1966) 1842;
(c) J.C. Calabrese, S. Trofimenko, J.S. Thompson, J. Chem. Soc., Chem. Commun.
(1986) 1122;
Acknowledgements
(d) S. Trofimenko, Prog. Inorg. Chem. 34 (1986) 115;
(e) K. Niedenzu, S. Trofimenko, Top. Curr. Chem. 131 (1986) 1;
(f) M.D. Curtis, K.-B. Shiu, W.M. Butler, J. Am. Chem. Soc. 108 (1986) 1550;
(g) S. Trofimenko, J.C. Calabrese, J.S. Thompson, Inorg. Chem. (1987) 1508;
(h) I.B. Gorrell, G. Parkin, Inorg. Chem. 29 (1990) 2452;
(i) R. Han, A. Looney, G. Parkin, J. Am. Chem. Soc. 111 (1989) 7276;
(j) R. Han, G. Parkin, J. Am. Chem. Soc. 112 (1990) 3662.
[6] C.A. Dodds, M.-A. Lehmann, J.F. Ojo, J. Reglinski, M.D. Spicer, Inorg. Chem. 43
(2004) 4927.
We are thankful to the DST (New Delhi) for funding under DST-
SERC (SR/S1/IC-0026/2007) project. We are thankful to Prof. J. H.
Huang of National Changhua University of Education, Changhua,
Taiwan for X-ray studies. The necessary laboratory and infrastruc-
tural facility are provided by the Department of Chemistry, Univer-
sity of Kalyani. The support of DST under FIST and UGC SAP
program to the Department of Chemistry, University of Kalyani is
acknowledged.
[7] (a) L.A. Huxham, E.L.S. Cheu, B.O. Patrick, B.R. James, Inorg. Chim. Acta 352
(2003) 238;
(b) Y.K. Yan, M. Melchart, A. Habtemariam, P.J. Sadler, Chem. Commun. (2005)
4764;
(c) A.F.A. Peacock, A. Habtemariam, R. Fernandez, V. Walland, F.P.A. Fabbiani, S.
Parsons, R.E. Aird, D.I. Jodrell, P.J. Sadler, J. Am. Chem. Soc. 128 (2006) 1739;
(d) R.E. Morris, R.E. Aird, P. Del Socorro Murdoch, H. Chen, J. Cummings, N.D.
Hughes, S. Parsons, A. Parkin, G. Boyd, D.I. Jodrell, P.J. Sadler, J. Med. Chem. 44
(2001) 3616;
(e) O. Novakova, H. Chen, O. Vrana, A. Rodger, P.J. Sadler, V. Brabec,
Biochemistry 42 (2003) 11544;
(f) H. Chen, J.A. Parkinson, R.E. Morris, P.J. Sadler, J. Am. Chem. Soc. 125 (2003)
173;
(g) R. Fernandez, M. Melchart, A. Abtemariam, S. Parsons, P.J. Sadler, Chem. Eur.
J. 10 (2004) 5173;
(h) B. Boardman, M.J. Hanton, H.V. Rensburg, R.P. Tooze, Chem. Commun.
(2006) 2289.
Appendix A. Supplementary material
Supplementary material CCDC 763726, 763727, 763728 and
763729 contain the supplementary crystallographic data for com-
plexes [(L1sal)Ru(CO)(Cl)(PPh3)], [(L1sal)2Ru] and [(L1nap)Ru
(CO)(Cl)(PPh3)] and (OL)Ru(PPh3)Cl. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. UV–Vis, IR spectra and 1H
NMR spectra of all the new complexes are given in Figs. S1–S41. Sup-

P. Pattanayak et al. / Inorganica Chimica Acta 363 (2010) 2865–2873
2873
[8] (a) M.C. van Engelen, H.T. Teunissen, J.G. De Vries, C.J. Elsevier, J. Mol. Catal. A:
Chem. 206 (2003) 185;
(b) H.T. Teunissen, C.J. Elsevier, Chem. Commun. (1997) 667.
[9] (a) R.A. Grey, G.P. Pez, A. Wallo, J. Am. Chem. Soc. 103 (1981) 7536;
(b) R.A. Grey, G.P. Pez, J. Corsi, A. Wallo, J. Chem. Soc., Chem. Commun. (1980)
783;
(c) R.A. Grey, G.P. Pez, Fundam. Res. Homogeneous Catal. 4 (1984) 97;
(d) R.A. Grey, G.P. Pez, Prepr. – Am. Chem. Soc., Div. Pet. Chem. 25 (1980) 399.
[10] (a) U. Matteoli, G. Menchi, M. Bianchi, F. Piacenti, P. Frediani, J. Mol. Catal. 22
(1984) 353;
(c) K. Nomura, H. Ogura, Y. Imanishi, J. Mol. Catal. A: Chem. 166 (2001) 345;
(d) K. Nomura, H. Ogura, Y. Imanishi, J. Mol. Catal. A: Chem. 178 (2002) 105;
(e) Y. Hara, H. Inagaki, S. Nishimura, K. Wada, Chem. Lett. (1992) 1983.
[12] P. Pattanayak, J.L. Pratihar, D. Patra, A. Burrows, M. Mohan, S. Chattopadhyay,
Eur. J. Inorg. Chem. (2007) 4263.
[13] J.L. Pratihar, S. Bhaduri, P. Pattanayak, D. Patra, S. Chattopadhyay, J.
Organomet. Chem. 694 (2009) 3401.
[14] (a) S. Halder, R. Acharyya, S.-M. Peng, G.-H. Lee, M.G.B. Drew, S. Bhattacharya,
Inorg. Chem. 45 (2006) 9654;
(b) S. Nag, P. Gupta, R.J. Butcher, S. Bhattacharya, Inorg. Chem. 43 (2004) 4814.
[15] P. Pattanayak, J.L. Pratihar, D. Patra, S. Mitra, A. Bhattacharyya, H.M. Lee, S.
Chattopadhyay, Dalton Trans. (2009) 6220.
(b) U. Matteoli, G. Menchi, M. Bianchi, P. Frediani, F. Piacenti, J. Mol. Catal. 29
(1985) 269;
(c) U. Matteoli, G. Menchi, M. Bianchi, F. Piacenti, J. Mol. Catal. 44 (1988) 347;
(d) U. Matteoli, G. Menchi, M. Bianchi, F. Piacenti, S. Ianelli, M. Nardelli, J.
Organomet. Chem. 498 (1995) 177.
[16] A.I. Vogel, A.R. Tatchell, B.S. Furnis, A.J. Hannaford, Vogel’s Textbook of
Practical Organic Chemistry, Longman (ELBS), fifth ed., 1996, p. 993.
[17] (a) N. Ahmed, J.J. Levison, S.D. Robinson, M.F. Uttlky, E.R. Wonchoba, G.W.
Parshall, Inorg. Synth. 15 (1974) 45;
(b) T.A. Stephenson, G. Wilkinson, J. Inorg. Nucl. Chem. 28 (1966) 945.
[18] G.M. Sheldrick, Acta Crystallogr. A64 (2008) 112.
[11] (a) U. Matteoli, G. Menchi, M. Bianchi, F. Piacenti, J. Organomet. Chem. 299
(1986) 233;
(b) U. Matteoli, G. Menchi, M. Bianchi, F. Piacenti, J. Mol. Catal. 64 (1991) 257;