Synthesis and characterization of some metal carbonyls with 2-hydroxyacetophenone ethanesulfonylhydrazone

Article abstract of DOI:10.1016/S1387-7003(03)00152-7

Five new complexes, [M(CO)₅(apesh)] [M = Cr; (1), Mo; (2), W; (3)], [Re(CO)₄ Br(apesh)] (4) and [Mn(CO)₃(apesh)] (5) have been synthesized by the photochemical reaction of metal carbonyls [M(CO)₆] (M = Cr, Mo, W), [Re(CO)₅ Br], and [Mn(CO)₃ Cp] with 2-hydroxyacetophenone ethanesulfonylhydrazone (apesh). The complexes have been characterized by elemental analysis, mass spectrometry, FT-IR, ¹H NMR spectroscopy. The spectroscopic studies show that apesh behaves as a monodentate ligand coordinating via imine N donor atom in (1)-(4) and as tridentate ligand in (5).

Full text of DOI:10.1016/S1387-7003(03)00152-7

Inorganic Chemistry Communications 6 (2003) 926–929
www.elsevier.com/locate/inoche
Synthesis and characterization of some metal carbonyls with
2-hydroxyacetophenone ethanesulfonylhydrazone
a,c,
b
a
b
*
€
€
€
, Ummuhan Ozdemir , Sema Sert , Nurcan Karacan ,
€
Ozan Sanlı Sßenturk
a
ꢀ
Fadime Ugur (Sarikahya)
a
_
Department of Chemistry, Faculty of Science, Ege University, Bornova, Izmir 35100, Turkey
Department of Chemistry, Faculty of Science and Literature, Gazi University, Teknikokullar, Ankara 06500, Turkey
b
c
Steacie Institute for Molecular Sciences, National Research Council of Canada, 100 Sussex Drive, Ottawa, Ottawa, Ont., Canada K1A 0R6
Received 2 February 2003; accepted 7 April 2003
Abstract
Five new complexes, [M(CO)5(apesh)] [M ¼ Cr; (1), Mo; (2), W; (3)], [Re(CO)4 Br(apesh)] (4) and [Mn(CO)3(apesh) ] (5) have
been synthesized by the photochemical reaction of metal carbonyls [M(CO)6] (M ¼ Cr, Mo, W), [Re(CO)5 Br], and [Mn(CO)3 Cp]
with 2-hydroxyacetophenone ethanesulfonylhydrazone (apesh). The complexes have been characterized by elemental analysis, mass
1
spectrometry, FT-IR, H NMR spectroscopy. The spectroscopic studies show that apesh behaves as a monodentate ligand coor-
dinating via imine N donor atom in (1)–(4) and as tridentate ligand in (5).
Ó 2003 Elsevier Science B.V. All rights reserved.
Keywords: Photosubstituton; 2-Hydroxyacetophenone ethanesulfonylhydrazone; Metal carbonyls
1. Introduction
complexes, which may have a chiral metalcenter or a
chiral coordinated ligand or both, have been employed
[19,20]. In view of the above, we have investigated a
series five new complexes (1–5) have been prepared for
the first time, by the photochemical reaction of metal
carbonyls [M(CO)6] (M ¼ Cr, Mo, W), [Re(CO)5 Br],
[Mn(CO)3 Cp] with 2-hydroxyacetophenone etha-
nesulfonylhydrazone (apesh).
There is growing pharmaceutical and chemical interst
in compounds containing the sulfonylhydrazine moiety
[1–9]. The numerous compounds containing a sulfon-
amide group or a hydrazine residue, or their combina-
tion in one molecule, show cytostatic and antibacterial
activity [10,11].
The Schiff base metal carbonyl complexes have con-
tinued to attract attention in part because of the dif-
ferent possible coordination geometries which the
ligand may adopt [12–14]. Their low energy metal-to-
ligand charge transfer (MLCT) transitions make these
molecules attractive for luminescence and electron
transfer reactions [15]. Besides this, several of these
complexes have been shown to be effective catalysts in
allylic alkylation reactions [16,17] and in the activation
of aromatic carbon–hydrogen bonds (orthometallation)
via intramolucular g2-bonding of arenes [18]. For
streoselective organic transformations, chiral metal
2. Experimental
2.1. General
Reactions were carried out under dry nitrogen using
Schlenk techniques. All solvents were dried and de-
gassed prior to use. Elemental analyses were carried out
using a LECO-CHNS-O-9320 by Technical and Scien-
* Corresponding author. Tel.: +1-613-9905836; fax: +1-613-9545242.
E-mail address: ozan.senturk@nrc.ca (O. Sanlı Senturk).
¨
1387-7003/03/$ - see front matter Ó 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S1387-7003(03)00152-7

O. Sanlı Sßent€urk et al. / Inorganic Chemistry Communications 6 (2003) 926–929
927
_
tific Research Council of Turkey, TUBITAK. FT-IR
spectra were recorded on samples in hexane at the Ege
University on a Mattson 1000 FT spectrophotometer.
1H NMR spectra were recorded in CDC13 on DMSO
on 400 MHz High Performance Digital FT-NMR at
CO), 1970 (m, CO), 1947 (s, CO), 1925 (s, CO), 1873 (m,
CO), 1605 (m, C@N), 1238 (s, CO). 1H NMR (d,
DMSO) ¼ 2.21 (CH3C@N, s,), 3.13 (CH2–S, s), 1.17
(CH3–CH2, s), 6.81–6.73, (C6H4, m), 10.42 (NH, s), OH
(11.63, s). MS (EI, 70 eV): m=z (%) ¼ 435(10),
TUBITAK. Electron impact mass Spectroscopy; Mi-
cromass VG Platform-II LC-MS were recorded at
_
TUBITAK. UV irradiations were performed with a
[Mþ ) (Me + CO)];
407(15),
[Mþ ) (Me + 2CO)];
_
379(20), [Mþ ) (Me + 3CO)]; 351(22), [Mþ ) (Me +
4CO)]; 323(28), [Mþ ) (Me + 5CO)].
medium-pressure 400 W mercury lamp through a
quartz-walled immersion well reactor.
W(apesh)(CO)5, (3): Yield (80%). Anal. Calc. C,
31.80, H, 2.47, N, 4.64, S, 5.65. Found C, 31.45, H, 2.59,
N, 4.61, S, 5.25. IR (m, KBr) ¼ 3210 (s, NH), 2069 (m,
CO), 1970 (m, CO), 1947 (s, CO), 1925 (s, CO), 1873 (m,
CO), 1605 (m, C@N), 1238 (s, CO). 1H NMR (d,
DMSO) ¼ 2.19 (CH3C@N, s,), 3.14 (CH2–S, s), 1.24
(CH3–CH2, s), 6.77–6.74, (C6H4, m), 10.41 (NH, s), OH
(11.57, s). MS (EI, 70 eV): m=z (%) ¼ 508(15),
Pentane, benzene, hexane, dichloromethane, acetone,
ethyl alcohol, diethylether, 2-hydroxyacetophenone,
ethanesulfonyl chloride, hydrazine hydrate, silica gel
were purchased from Merck and M(CO)6 (M ¼ Cr, Mo,
W), Re(CO)5Br and Mn(CO)3Cp were purchased from
Aldrich. These reagents were used as supplied. 2-hy-
droxyacetophenone ethanesulfonylhydrazone (apesh)
were prepared by the literature method [9].
[Mþ ) (2Me + CO)];
480(25),
[Mþ ) (2Me + 2CO)];
452(20),[Mþ ) (2Me + 3CO)]; 396(20), [Mþ ) (2Me +
5CO)].
2.2. Synthesis
Re(apesh)(CO)4Br, (4): Yield (77%). Anal. Calc. C,
27.10, H, 2.27, N, 4.52, S, 5.17. Found C, 26.95, H, 2.06,
N, 4.75, S, 5.58. IR (m, KBr) ¼ 3211 (s, NH), 2112 (w,
CO), 2023 (m, CO), 1918 (m, CO), 1909 (m, CO), 1605
The complexes, [M(CO)5(apesh)] [M ¼ Cr; (1), Mo;
(2), W; (3)], [Re(CO)4Br(apesh)] (4), and [Mn(CO)3
(apesh) ] (5) were prepared by the photochemical reac-
tions of metal carbonyls M(CO)6 (M ¼ Cr, Mo,W),
Re(CO)5Br and Mn(CO)3Cp with 2-hydroxyacetophe-
none ethanesulfonylhydrazone (apesh) and were ob-
tained in 70–80% yields by similar methods of which the
following is typical.
1
(m, C@N), 1237 (s, CO). H NMR (d, DMSO) ¼ 2.21
(CH3C@N, s), 3.14 (CH2–S, s), 1.24 (CH3–CH2, s),
6.88–6.55, (C6H4, m), 10.41 (NH, s), OH (11.58, s). MS
(EI, 70 eV): m=z (%) ¼ 534(20), [Mþ ) (2Me + 2CO)];
506(25), [Mþ ) (2Me + 3CO)]; 478(25), [Mþ ) (2Me +
4CO)].
The complex Cr(CO)6 (0.44 g, 2 mmol) and apesh
(0.48 g, 2 mmol) were dissolved in tetrahydrofuran (80–
100 ml). The solution was irradiated for 2 h. During the
irradiation, the color of the reaction mixture changed
from colorless to dark yellow. After the irradiation, the
reaction mixture was evaporated under vacuum, yield-
ing a dark yellow solid. After dissolving in dichlorom-
ethane (10 ml), 50 ml of petroleum ether was added,
resulting in the precipitation of a dark yellow solid
which was washed with petroleum ether and dried under
vacuum. Yield of [Cr(CO)5(apesh)]:76%. The composi-
tion of the compounds are confirmed by elemental
analysis and EI MS.
Mn(apesh)(CO)3, (5): Yield (74%). Anal. Calc. C,
40.94, H, 3.67, N, 7.34, S, 8.39. Found C, 40.55, H, 3.88,
N, 7.56, S, 8.12 IR (m, K Br)¼ 2020 (s, CO), 1975 (s,
1
CO), 1928 (m, CO), 1602 (m, C@N), 1246 (s, CO). H
NMR (d, DMSO): 2.09 (CH3C@N, s,), 3.16 (CH2–S, s),
1.24 ( CH3–CH2, s), 6.75–7.48, (C6H4, m), 12.55 (NH,
s). MS (EI, 70 eV): m=z (%) ¼ 381 (100) 366(10),
[Mþ ) (Me)]; 338(15), [Mþ ) (Me + CO)]; 310(15),
[Mþ ) (Me + 2CO)]; 282(25), [Mþ ) (Me + 3CO)].
apesh: IR (m, KBr) ¼ 3213 (s, NH), 1622 (m, C@N),
1238 (s, CO), 1339 (s, asSO2), 1167 (s, sSO2). 1H
NMR(d, DMSO) ¼ 2.32 (CH3C@N, s), 3.22 (CH2–S, s),
1.27 (CH3–CH2, s), 6.87–7.52, (C6H4, m), 10.61 (NH, s),
OH (11.69, s) taken from [9]
Cr(apesh)(CO)5, (1): Yield (76%). Anal. Calc. C,
41.47, H, 3.22, N, 6.45, S, 7.37. Found C, 40.22, H, 3.05,
N, 6.67, S, 7.26. IR (m, KBr): 3211 (s, NH), 2071 (m,
CO), 1971 (m, CO), 1948 (s, CO), 1937 (s, CO), 1873 (m,
CO), 1606 (m, C@N), 1237 (s, CO). 1H NMR (d,
DMSO) ¼ 2.21 (CH3 C@N, s,), 3.12 (CH2–S, s), 1.26
(CH3–CH2, s), 6.78–6.76, (C6H4, m), 10.40 (NH, s), OH
(11.70, s). MS (EI, 70 eV): m=z (%) ¼ 391(15), [Mþ )
(Me + CO)]; 363(20), [Mþ ) (Me + 2CO)]; 335(20),
3. Results and discussion
Complexes (1–5) were prepared by a photochemical
reaction as shown in Scheme 1. The photogeneration of
M(CO)5 from M(CO)6 (M ¼ Cr, Mo,W) has been ex-
tensively studied. These 16-electron M(CO)5 fragments
react quickly with any available donor atom to form
M(CO)5L species. If L is a bidentate ligand, M(CO)4L
chelate or bridging M2(CO)10(l-L) compounds may
occur [21–23]. In this study, photochemical reactions of
M(CO)6(M ¼ Cr, Mo, W), Re(CO)5Br with apesh ligand
[Mþ ) (Me + 3CO)];
307(10),
[Mþ ) (Me + 4CO)];
279(10), [Mþ ) (Me + 5CO)].
Mo(apesh)(CO)5, (2): Yield (79%). Anal. Calc. C,
37.65, H, 2.92, N, 5.85, S, 6.35. Found C, 37.81, H, 2.67,
N, 5.59, S, 6.35. IR (m, KBr): 3210 (s, NH), 2069 (m,

928
O. Sanlı Sßent€urk et al. / Inorganic Chemistry Communications 6 (2003) 926–929
Scheme 1. The photochemical reactions of M(CO)6 (M ¼ Cr, Mo, W), Re(CO)5Br and [Mn(CO)3Cp] with apesh ligand.
proceed in this expected manner, and gave a series of
complexes (1–4) and however, the formation of
[Mn(CO)3(apesh)], (5), occurs via displacement of the
anionic cyclopentadienide ligand (C5H5)ꢀ.
withdrawing groups, tends to resonate at higher fre-
quencies. In addition, the shift of the C–O stretching
vibration in the IR spectrum shows that both imine N
and phenolic O donor atoms coordinate to Mn atom.
Kinematic coupling of the CO group with the bonded
metal ion would increase the frequencies [30]. According
to the these data, the salesh ligand behaves as tridentate
and ionic ligand in (5). The apesh ligand must act as a 6-
electron donor in order to satisfy the 18-electron rule.
The mass spectra show fragmentation via successive
loss of CO groups and organic ligands.
The rather strong C@N stretching vibration, found at
1621 cmꢀ1 in the free ligand, shifts to lower wavenumber
in (1–5), showing that apesh ligand coordinates to the
metal via the imine donor atom [24]. This shift has been
explained as weakening of the CN bond resulting from
the loss of electron density from the nitrogen to the
metal atom [24]. No shifting upon complex formation
was observed at mas(SO2), msym(SO2), m(NH) and m(CO)
stretching vibrations indicating that SO2, NH and CO
group were not coordinated to metal atoms in (1–4). OH
stretching vibration was not observed both free ligand
and in (1–4) because of hydrogen bonding with the
imine nitrogen atom [9].
In summary, salesh behaves as monodentate ligand
via N imine donor atom in (1–4), but behaves as trid-
entate ligand via anionic O, imine N and amine N donor
atoms in (5).
According to number of carbonyl bands, provides
important clues to the environment of the metalcenters
[25]. Five carbonyl stretching bands in (1–3) are attrib-
uted to local C4v symmetry of M(CO)5 [21,22]. Similarly,
four CO stretching absorptions in (4) and three in (5)
indicate to local C2v [26], C3v [27] symmetry, respectively
(shown in Scheme 1). The m(CO) modes in (1–5) move
also to lower wave numbers when compared with the
starting carbonyl complexes [21,22].
Acknowledgements
We thank BP (Turkey) for the provision of photo-
chemical apparatus and Research Foundation of Ege.
This research was also supported by Gazi University
Research Found under Project No 05-98/24. We thank
_
TUBITAKfor allocation of time at the NMR, Mass
Spectra and Elemental Analyses.
In the 1H NMR spectra of (1–4), a downfield shift of
about 0.11 ppm for CH3C@N proton and 0.2 ppm for
NH proton relative to the free ligand were observed.
The small shifting is related to a decrease in p-electron
density in the C@N bond with complex formation in (1–
4). According to the these data, the apesh ligand behaves
as monodentate in (1–4). However, in the NMR spec-
trum of Mn(apesh)(CO)3, (5), the phenolic OHꢀ signal
disappeared which is in agreement with the formation of
Mn–O bond [28,29]. NH signal was found 1.94 ppm
downfield compared to the free ligand in (5). Because,
the coordination of NH to Mn atom, like electron
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