Photochemical complexation reactions of M(CO)6 (M=Cr, Mo, W) and Re(CO)5Br with rhodanine (4-thiazolidinone-2-thioxo) and 5-substituted rhodanines

Article abstract of DOI:10.1080/15533170601028116

The new complexes [M(CO)₅-DABRd] [M=Cr; 1, Mo; 2, W; 3], [cis-Re(CO)₄Br-DABRd] (4), [M(CO)₅-BRd] [M=Cr; 5, Mo; 6, W; 7] and [Mo(CO)₅-L] [L=Rd, 8; 2CBRd, 9; 2HNARd, 10; IBRd, 11] have been synthesized by the phot

Full text of DOI:10.1080/15533170601028116

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Photochemical Complexation Reactions of M(CO)6
(M=Cr, Mo, W) and Re(CO)5Br with Rhodanine
(4‐Thiazolidinone‐2‐thioxo) and 5‐Substituted
Rhodanines
Elif Subasi a , Ayse Ercag b , Sema Sert c & Ozan S. Senturk d
a Department of Chemistry, Faculty of Science and Literature , Dokuz Eylul University ,
Buca‐Tinaztepe, Izmir, Turkey
b Department of Chemistry, Engineering Faculty , Istanbul University , Istanbul, Turkey
c Department of Chemistry, Faculty of Science , Ege University , Bornova, Izmir, Turkey
d Department of Chemistry, Faculty of Science and Literature , Istanbul Technical
University , Maslak, Istanbul, Turkey
Published online: 15 Feb 2007.
To cite this article: Elif Subasi , Ayse Ercag , Sema Sert & Ozan S. Senturk (2006) Photochemical Complexation Reactions of
M(CO)6 (M=Cr, Mo, W) and Re(CO)5Br with Rhodanine (4‐Thiazolidinone‐2‐thioxo) and 5‐Substituted Rhodanines, Synthesis and
Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 36:10, 705-711
To link to this article: http://dx.doi.org/10.1080/15533170601028116
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Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, 36:705–711, 2006
Copyright # 2006 Taylor & Francis Group, LLC
ISSN: 0094-5714 print/1532-2440 online
DOI: 10.1080/15533170601028116
Photochemical Complexation Reactions of M(CO)6
(M 5 Cr, Mo, W) and Re(CO)5Br with Rhodanine
(4-Thiazolidinone-2-thioxo) and 5-Substituted Rhodanines
Elif Subasi
Department of Chemistry, Faculty of Science and Literature, Dokuz Eylul University, Buca-Tinaztepe,
Izmir, Turkey
Ayse Ercag
Department of Chemistry, Engineering Faculty, Istanbul University, Istanbul, Turkey
Sema Sert
Department of Chemistry, Faculty of Science, Ege University, Bornova, Izmir, Turkey
Ozan S. Senturk
Department of Chemistry, Faculty of Science and Literature, Istanbul Technical University, Maslak,
Istanbul, Turkey
INTRODUCTION
The new complexes [M(CO)5-DABRd] [M 5 Cr; 1, Mo; 2, W;
3], [cis-Re(CO)4Br-DABRd] (4), [M(CO)5-BRd] [M 5 Cr; 5, Mo;
6, W; 7] and [Mo(CO)5-L] [L 5 Rd, 8; 2CBRd, 9; 2HNARd, 10;
IBRd, 11] have been synthesized by the photochemical reactions
of VIB and VIIB group metal carbonyls [M(CO)6] [M 5 Cr,
Mo, W] and [Re(CO)5Br] with 5-(4-dimethylaminobenzylidene)r-
hodanine (DABRd), 5-benzylidenerhodanine (BRd), rhodanine
(Rd), 5-(2-chlorobenzylidene)rhodanine (2CBRd), 5-(2-hydroxy-
naphtylidene)rhodanine (2HNARd), 5-(4-isopropylbenzylidene)r-
hodanine (IBRd) and characterized by elemental analysis, FT-
The heterocyclic ligands that contain the C(55S)-NH-
fragment have continued to attract attention in part because
of their capability of thione-thiol tautomerism, usually
involves the evolution of the ligand towards its thiol form
and the formation of a strong M-S bond and a secondary
[1–3]
..
M N bond.
The nucleophilic activity of the methylene
carbon atom at position 5 of the rhodanine ring allows
reaction with electrophilic centers and the ready formation of
5-substituted derivatives.[4] Rhodanine derivatives have been
extensively investigated due to their use in analytical chemistry
and their biological activity. These compounds exhibit various
biological activities, particularly: antibacterial and bacterio-
static, fungucidal and fungustatic, antiparasitic, antitubercu-
lous and tuberculostatic, antiviral, antitumoral.[5–8]
1
IR, 1H and 13C-f Hg-NMR spectroscopy and by Mass spec-
trometry. The spectroscopic studies show that all rhodanine
ligands act as monodentate ligands coordinating via the sulfur
(C55S) donor atom in (1–11).
Keywords rhodanine (4-thiazolidinone-2-thioxo), 5-benzylidene-
rhodanines, metal carbonyl complexes, organometallic
compounds
Some derivatives of rhodanine were found to have higher
sensitivity and selectivity for the spectrophotometric analyses
of some noble metal ions and heavy metal ions.[9–12]
Rhodanine is coordinated through the thiocarbonylic sulfur
in the neutral form or through the thiocarbonylic sulfur and
the endocyclic nitrogen atoms in neutral or deprotonated
form.[13,14] Although many papers are available on the metal
complexes of 5-arylidenerhodanines, there is no previous
work on the carbonyl compounds.[15,16] Carbonyl compounds
with sulfur and nitrogen donor ligands continue to attract
considerable attention not only on account of their fascinating
structural chemistry, but also because of their ability to act
as electron reservoirs and their potential in catalysis.[17]
Received 15 July 2006; accepted 22 August 2006.
We thank BP (Turkey) for the provision of photochemical appar-
atus and Research Foundation of Ege and Dokuz Eylul University
for funds. We thank TUBITAK for allocation of time at the Mass
Spectra and Elemental Analyses. We thank Dr. Yurdanur Yayla for
1
obtaining 1H- and 13C-f Hg-NMR. spectra at Ege University. This
work also supported by Research Fund of Istanbul University,
Project Number: 818/190496, and Dokuz Eylul University, Project
Number: 04.KB.FEN.106.
Address correspondence to Elif Subasi, Department of Chemistry,
Faculty of Science and Literature, Dokuz Eylul University, Buca-
Tinaztepe, Izmir 35160, Turkey. E-mail: elif.subasi@deu.edu.tr
705

706
E. SUBASI ET AL.
Features of the chemistry of these molecules which are cur-
rently of interest include the mechanisms and sites of substi-
tution as well as the modification of reactivity accompanying
carbonyl replacement by donor ligands.[18]
As ligands, rhodanines have more than one potential donor
atoms. Therefore, we tried to observe the sites of substitution of
these ligands to the metal center. Along with our continued
interest in the photochemical synthesis and structural aspects
of group VIB and VIIB metal carbonyls led us to launch us
an exploratory investigation into the photolytic behaviour of
the VIB and VIIB metal carbonyls, [M(CO)6] [M ¼ Cr, Mo,
W] and [Re(CO)5Br] with the title ligands DABRd, BRd, Rd,
2CBRd, 2HNARd and IBRd which contain the pentagonal het-
erocycle rhodanine. In this paper, the hitherto unknown new
complexes [M(CO)5-DABRd] [M ¼ Cr; 1, Mo; 2, W; 3],
[cis-Re(CO)4Br-DABRd] (4), [M(CO)5-BRd] [M ¼ Cr; 5,
Mo; 6, W; 7] and [Mo(CO)5-L] [L ¼ Rd, 8; 2CBRd, 9;
2HNARd, 10; IBRd, 11] have been prepared by the photo-
chemical reactions of [M(CO)6] [M ¼ Cr, Mo, W] and
[Re(CO)5Br] with 5-(4-dimethylaminobenzylidene)rhodanine
(DABRd), 5-benzylidenerhodanine (BRd), rhodanine (Rd),
5-(2-chlorobenzylidene)rhodanine (2CBRd), 5-(2-hidroxyna-
phthylidene)rhodanine (2HNARd), 5-(4-isopropylbenzyli-
dene)rhodanine (IBRd) and characterized by elemental
1
analyses, FT-IR, 1H and 13C-f Hg-NMR spectroscopy and
Mass spectrometry. The spectroscopic studies show that the
rhodanine ligands act as monodentate ligands coordinating
via the sulfur (C55S) donor atom in (1–11).
EXPERIMENTAL
Reactions were carried out under a dry N2 atmosphere using
Schlenk techniques. All solvents were dried and degassed
using standard techniques.[19] Elemental analyses were per-
formed on a LECOCHNS-O-9320 instrument at Technical
and Scientific Research Council of Turkey, TUBITAK. FT-
IR spectra of samples were recorded in KBr at Dokuz Eylul
1
University on a Varian 1000 FT spectrophotometer. H- and
1
13C-f Hg-NMR spectra were recorded in CDCl3 on DMSO
on 500 MHz High Performance Digital FT-NMR instrument
at Ege University and chemical shifts were referenced to tetra-
methylsilane (TMS). Electron impact mass spectroscopy;
Micromass VG Platform-II LC-MS were recorded at
TUBITAK. UV irradiations were performed with a medium-
pressure 400 W mercury lamp through a quartz-walled
immersion well reactor.
Organic solvents and silica gel were purchased from Merck
and M(CO)6 (M ¼ Cr, Mo, W), [Re(CO)5Br], Rd and alde-
hydes were from Aldrich. DABRd, BRd, 2CBRd, 2HNARd
and IBRd were prepared by literature method.[20]
FIG. 1. The photogenerations of (1–11).
The complexes, [M(CO)5-DABRd] [M ¼ Cr; 1, Mo; 2, W; reactions of [M(CO)6] (M ¼ Cr, Mo, W) and [Re(CO)5Br]
3], [cis-Re(CO)4Br-DABRd] (4), [M(CO)5-BRd] [M ¼ Cr; 5, with DABRd, BRd, Rd, 2CBRd, 2HNARd and IBRd and
Mo; 6, W; 7] and [Mo(CO)5-L] [L ¼ Rd, 8; 2CBRd, 9; obtained in 55–82% yield by similar methods of which the
2HNARd, 10; IBRd, 11] were prepared by the photochemical following is typical.

PHOTOCHEMICAL COMPLEXATION REACTIONS OF RHODANINES
707
TABLE 1
Elemental analysis results and physical properties of the complexes (1–11)
Elementel analyses found (Calcd.) (%)
Empirical formula
(formula weight)
Complexa
Yield (%)
C
H
N
S
1
2
3
4
5
6
7
8
9
C17H12CrN2O6S2 (456.0)
C17H12MoN2O6S2 (499.9)
C17H12WN2O6S2 (587.8)
C16H12ReN2O5S2Br (642.2)
C15H7CrNO6S2 (413.0)
C15H7MoNO6S2 (456.9)
C15H7WNO6S2 (544.8)
C8H3MoNO6S2 (368.9)
C15H6MoNO6S2Cl (491.4)
C19H9MoNO7S2 (522.9)
C19H15MoNO6S2 (512.9)
73
82
70
68
66
65
72
66
74
62
55
46.22 (44.73)
42.04 (40.80)
35.59 (34.71)
30.51 (29.89)
43.51 (43.58)
39.11 (39.39)
33.00 (33.03)
25.95 (26.00)
36.36 (36.62)
43.00 (43.60)
32.25 (44.45)
2.54 (2.63)
2.49 (2.40)
2.02 (2.04)
1.88 (1.87)
1.26 (1.69)
1.22 (1.53)
1.19 (1.28)
0.75 (0.81)
1.10 (1.22)
1.70 (1.72)
2.78 (2.92)
6.24 (6.14)
5.69 (5.60)
4.81 (4.76)
4.50 (4.36)
3.23 (3.39)
3.03 (3.06)
2.23 (2.57)
3.60 (3.79)
12.54 (12.85)
2.44 (2.68)
2.69 (2.73)
14.40 (14.03)
13.16 (12.80)
11.12 (10.88)
10.18 (9.97)
15.33 (15.49)
13.88 (14.00)
11.52 (11.74)
17.05 (17.34)
12.98 (13.02)
12.02 (12.23)
12.34 (12.48)
10
11
aReddish brown.
The complexes Cr(CO)6 (0.44 g, 2 mmol) and DABRd solid which was extracted with CH2Cl2 (10 mL). Addition of
(0.54 g, 2 mmol) were dissolved in THF (80–100 mL) and petroleum ether (50 mL) resulted in precipitation of a dark
the solution was irradiated for 2 hr using a 400 W medium brown solid which was washed with petroleum ether and
pressure mercury lamp through a quartz-walled immersion dried under vacuum, and shown to be [Cr(CO)5-DABRd]
well reactor. During the irradiation, the solution changed (0.12 g, 73% yield). Traces of unreacted hexacarbonylchro-
from colourless to redish-brown. After irradiation the solvent mate(0) was sublimed out in vacuum on a cold finger at
was evaporated under the vacuum yielding a redish-brown 2208C while keeping the complex at 08C in an ice bath.
TABLE 2
Important infrared spectral bands (cm21) of the ligands and their complexes
Complex
n(CO)
n(C55S)
n(NH)
n(C55O)
n(C-Sring)
HDABRda
BR
Rd
—
—
—
—
—
—
685 s, 610 s
677 s, 602 s
681 s, 606 s
674 s, 633 s
685 s, 610 s
675 s, 602 s
3150 m, 3060 m
3165 m, 3072 m
3166 m, 3083 m
3149 m, 3067 m
3170 m, 3067 m
3146 m, 3051 m
1690 s
1695 s
1710 s
1693 s
1690 s
1690 s
810 s
816 s
822 s
814 s
810 s
820 s
2CBRd
2HNARd
IBRd
1
2
3
4
5
6
7
8
9
2060 s, 1972 s, 1940 s, 1917 s, 1886 m
2069 s, 1963 s, 1931 s, 1906 s, 1898 m
2068 s, 1969 s, 1942 s, 1910 s, 1880 m
2106 m, 2024 m, 1920 m, 1892 m
730 s, 578 s
716 s, 556 s
703 s, 586 s
697 s, 594 s
694 s, 520 s
722 s, 581 s
724 s, 585 s
735 s, 593 s
695 s, 603 s
691 s, 587 s
690 s, 584 s
3150 m, 3060 m
3150 m, 3060 m
3150 m, 3060 m
3150 m, 3060 m
3160 m, 3070 m
3165 m, 3070 m
3165 m, 3072 m
3165 m, 3085 m
3150 m, 3065 m
3168 m, 3063 m
3142 m, 3050 m
1689 s
1690 s
1688 s
1690 s
1695 s
1690 s
1690 s
1709 s
1690 s
1690 s
1690 s
810 s
805 s
816 s
812 s
817 s
815 s
810 s
816 s
810 s
805 s
816 s
2070 s, 1970 s, 1940 s, 1916 s, 1880 m
2069 s, 1969 s, 1942 s, 1910 s, 1886 m
2070 s, 1974 s, 1940 s, 1910 s, 1886 m
2070 m, 1972 s, 1946 s, 1935 s, 1870 m
2072 s, 1971 m, 1948 m, 1937 s, 1873 s
2075 s, 1970 s, 1946 s, 1937 s, 1872 s
2070 s, 1972 m, 1945 s, 1936 s, 1870 s
10
11
aTaken from Ref. [3].

TABLE 3
1
1H- and 13C-f Hg-NMR data for the ligands and their complexes in DMSO-d6 solutiona
DABRd BRd
Rd 2CBRd 2HNARd IBRd
1
2
3
4
5
6
7
8
9
10
11
1H-n.m.r.
d(N(3)-H)
d(C(6)-H)
13C-n.m.r.
d[C(2)]
d[C(4)]
d[C(5)]
d[C(6)]
d[ax.(CO)]
d[eq.(4CO)]
d[eq.(2CO)]
d[eq.&ax(CO)]
13.56 sb 13.55 s 13.56 s 13.50 s 13.60 s 13.56 s 13.56 s 13.56 s 13.55 s 13.50 s 13.55 s 13.48 s 13.50 s 13.55 s 13.50 s 13.60 s 13.54 s
7.49 sb 7.50 s
7.84 s 7.80 s 7.49 s 7.52 s 7.52 s 7.50 s 7.50 s 7.50 s 7.52 s 7.50 s 7.48 s 7.84 s 7.79 s 7.47 s
—
195.1 sb 204.5 s 195.1 212.7
169.5 sb 172.4 s 169.5 176.2
117.4 sb 122.3 s 117.4 127.5
133.5 sb 142.4 s 133.5 140.5
220.1
193.9 207.4 s 206.2 s 209.1 s 210.5 s 212.2 s 213.1 s 210.4 s 176.8 198.6 195.9
171.8 171.9 s 170.0 s 170.4 s 169.6 s 171.2 s 172.5 s 172.4 s 171.8 174.5 183.0
123.2 118.7 s 119.1 s 119.5 s 117.7 s 121.2 s 122.4 s 122.3 s 114.4 127.8 132.0
138.5 135.2 s 133.7 s 134.5 s 134.2 s 142.5 s 143.5 s 142.1 s 133.0 143.5 153.7
174.3
170.5
122.1
136.5
222.8
200.6
—
182.1
134.4
152.6
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
220.4 s 216.8 s 207.2 s
214.2 s 205.0 s 194.3 s
—
—
217.3 s 222.4 s 218.9 s 224.2 218.3 226.9
209.2 s 198.0 s 186.5 s 205.4 201.2 203.5
—
—
—
—
—
—
—
—
215.6 s
218.2 s,
186.4 s
—
—
—
—
—
—
—
—
—
—
—
—
—
—
ad in ppm, J in Hz.
bTaken from Ref. [3].

PHOTOCHEMICAL COMPLEXATION REACTIONS OF RHODANINES
709
RESULTS AND DISCUSSION
vibrations of C-Sring observed at 810–816 cm21 in the free
ligands shift to just slightly lower wave numbers in the
spectra of the (1–11). The divisions between strong symmetric
and asymmetric stretching vibrations of C55S in DABRd, BRd,
Rd, 2CBRd, 2HNARd and IBRd are increased in the spectra of
the (1–11), showing that the rhodanine ligands coordinate to
the metal via their sulfur (C55S) atoms in (1–11). Important
FT-IR spectral data of (1–11) are presented in Table 2. As
expected, five bands arising from n(CO) vibrations are seen
for complexes (1–3 and 5–11) which presumably have the
local C4v (2A1 þ E) symmetry of the M(CO)5 unit (M ¼ Cr,
Mo, W). Similarly, there are four CO stretching mode in the
IR spectra of (4). According to IR spectra, the Re(CO)4 unit
in compound (4) has local C2v(2A1 þ B1þB2) symmetry.[17,33]
The n(CO) modes of (1–11) move to lower wave numbers
when compared with the starting M(CO)6 (M ¼ Cr, Mo, W)
and [Re(CO)5Br] molecules.[17,28–32]
Recently, photogeneration of M(CO)5 from M(CO)6
(M ¼ Cr, Mo, W) has been extensively studied.[21–27] These
16-electron containing M(CO)5 fragments react avidly with
any available donor to form M(CO)5L species, where L is a
chelating bidentate ligand, and rapid continuation to the
chelating M(CO)4L or bridging M2(CO)10-L products may
occur. Moreover, photogeneration of M(CO)4 (M ¼ Re),
M(CO)3 and M(CO)2 (M ¼ Mn) from [Re(CO)5Br] and
[Mn(CO)3Cp] have been synthesized by our working
group.[17,28–32] The photochemical reactions of M(CO)6
(M ¼ Cr, Mo, W) and [Re(CO)5Br] with DABRd and of
M(CO)6 (M ¼ Cr, Mo, W) with BRd, Rd, 2CBRd, 2HNARd
and IBRd proceed in this expected manner to yield the
previously unknown series of complexes (1–11) in Figure 1.
The analytical results and some physical properties of the
novel complexes (1–11) are summarized in Table 1.
The changes observed in the FT-IR spectrum of the free
ligands upon coordination may be compared with the spectral
changes in rhodanine in its metal carbonyl complex. The
n(N-H) ligand bands at 3150 and 3060 cm21 appear, as
expected for N(3)-H of DABRd, BRd, Rd, 2CBRd, 2HNARd
and IBRd in the complexes (1–11). All of the complexes
exhibit no changes in the intensity or position of the bands in
the range 1700–1660 cm21 that are indicative of coordination
via n(C55O), this is in keeping with there are no metal ¼
oxygen interactions in these complexes. The stretching
1
1H- and 13C-f Hg-NMR spectra data in DMSO-d6 solutions
of compounds (1–11) are listed in Table 3 together with the
assignments of the signals. The presence of the low field
N(3)-H signal in the 1H-NMR spectra of the complexes
(1–11) indicate that deprotonation of the ligands from their
N(3)-H on coordination to the organometallic moiety is not
1
possible. It was clearly seen from the 13C-f Hg-NMR spectra
that the coordination of the ligand to the metal from (C55S)
sulfur atom, deshields the thiazolidine ring carbons. The
relatively slight deshielding of C(2) is compatible with the
TABLE 4
The mass spectral data of (1–11)
Complex
M.W.
456
Relative intensities of the ions m/e
1
456 (5), [Mþ]; 428 (15), [Mþ-(CO)]; 400 (27), [Mþ-2(CO)]; 372 (20), [Mþ-3(CO)]; 316 (25),
[Mþ-5(CO)].
2
3
4
5
6
7
499.9
587.8
642.2
413
500 (7), [Mþ]; 444 (15), [Mþ-2(CO)]; 416 (22), [Mþ-3(CO)]; 388 (15), [Mþ-4(CO)]; 360 (12),
[Mþ-5(CO)].
588 (10), [Mþ]; 560 (14), [Mþ-(CO)]; 532 (20), [Mþ-2(CO)]; 504 (20) [Mþ-3(CO)]; 476 (15),
[Mþ-4(CO)]; 448 (20) [Mþ-5(CO)].
642 (5), [Mþ]; 534 (10), [Mþ-(CO)-Br]; 506 (20), [Mþ-2(CO)-Br]; 478 (15) [Mþ-3(CO)-Br];
450 (12), [Mþ-4(CO)-Br].
413 (10), [Mþ]; 385 (15), [Mþ-(CO)]; 357 (24), [Mþ-2(CO)]; 329 (18) [Mþ-3(CO)]; 301 (26),
[Mþ-4(CO)]; 273 (15), [Mþ-5(CO)].
456.9
544.8
457 (12), [Mþ]; 429 (20), [Mþ-(CO)]; 401 (14), [Mþ-2(CO)]; 373 (15) [Mþ-3(CO)]; 345 (10),
[Mþ-4(CO)]; 317 (12), [Mþ-5(CO)].
545 (8), [Mþ]; 517 (15), [Mþ-(CO)]; 489 (22), [Mþ-2(CO)]; 461 (18) [Mþ-3(CO)]; 433 (14),
[Mþ-4(CO)]; 405 (10), [Mþ-5(CO)].
8
9
10
11
368.9
491.4
522.9
512.9
369 (102), [Mþ]; 313 (15) [Mþ-2(CO)]; 257 (30), [Mþ-4(CO)]; 229 (10), [Mþ-5(CO)].
491.4 (20), [Mþ]; 436 (15), Mþ-2(CO)]; 379 (20), [Mþ-4(CO)]; 352 (25), [Mþ-5(CO)].
523 (10), [Mþ]; 495 (10) [Mþ-CO]; 411 (15), [Mþ-4(CO)].
513 (15), [Mþ]; 457 (15), [Mþ-2(CO)]; 429 (15), [Mþ-3(CO)]; 373 (20), [Mþ-5(CO)].
For the mass spectral data relative intensities are given in parentheses; probable assignments in square bracket.

710
E. SUBASI ET AL.
7. Suzen, S.; Buyukbingol, M. Recent studies of aldose reductase
enzyme inhibition for diabetic complications. Curr. Med. Chem.
2003, 10 (15), 1329.
maintenance of the thione form of the ligand in solution,
because conversion to the thiol form would result in stronger
shielding as in the S-coordinated methyl- and phenylmercur-
y(II) complexes of rhodanine [HgR(Rd)].[17,34]
8. Vajpai, R.; Tiwari, B. M. L.; Tiwari, K. S. A comparative study of
synthesis, characterisation and applications of 5-(salicylidene)
rhodanine and 5-(2-hydroxy naphthalidene) rhodanine. Asian
J. Chem. 1999, 11 (2), 414.
The mass spectral data of (1–11) are given in Table 4, and
show fragmentation via successive loss of CO groups and
organic ligands. For the mass spectral data relative intensities
are given in parantheses; probable assignments in square
brackets. For all assignments the most abundant isotopes of
Cr, Mo, W and Re have been selected (52Cr, 83.76%; 98Mo,
24%; 184W, 30.7%; 187Re, 62.9% abundant).
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We have presented the novel photochemical reactions
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2CBRd, 2HNARd and IBRd. The spectroscopic studies show
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coordinating via their (C55S) atom in (1–11) and behave as a
two-electron donor in order to satisfy the 18-electron rule in
metal carbonyl complexes (1–11). Furthermore, the n(CO)
modes move to low wave number when compared with the
starting M(CO)6 (M ¼ Cr, Mo, W) and [Re(CO)5Br] mol-
ecules. Apparently, the metallation cause the deshielding of
¨
11. Turak, F.; Ozgu¨r, M.; Erc¸ag, A. Simultaneous determination of
˘
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1
1
all the carbons of the pentagonal ring in H- and 13C-f Hg-
NMR spectra. The mass spectra of the complexes (1-11)
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mentation of the DABRd, BRd, Rd, 2CBRd, 2HNARd and
IBRd ligands.
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17. (a) Sert, S.; Ercag, A.; Senturk, O. S.; Sterenberg, B. T.;
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(b) Vahrenkamp, Muller, A., Krebs, B., Eds., Sulfur: its signifi-
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Technology; Elsevier: Amsterdam, 1984; (c) Adams, R. D.;
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carbonyl cluster. The Addition of H2 to Os4(CO)11(m4-S)(m4-
HCCCO2Me). Organometallics 1986, 5, 1272.
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