Photochemical reactions of Re(CO)5Br with tetraalkyldiphosphine disulfides (R = Me, Et, nPr, nBu, Ph) and the crystal structure of [ReBr(CO)3(Et2P(S)P(S)Et2)]

Article abstract of DOI:10.1016/S0277-5387(03)00327-9

The hitherto unknown series of complexes fac-[Re(CO)₃Br{R₂P(S)P(S)R₂}] 1a-5a (1a, R = Me; 2a, R = Et; 3a, R = ⁿPr; 4a, R = ⁿBu; 5a, R = Ph) and [Re₂(CO)₈Br₂{cis-μ-R₂P(S) P(S)R₂}] 1b-5b [lb, R = Me; 2b, R = Et; 3b, R = ⁿPr; 4b, R = ⁿBu; 5b, R = Ph] have been prepared by the photochemical reaction of Re(CO)₅Br with R₂P(S)P(S)R₂. The complexes have been characterized by elemental analysis, mass spectroscopy (EI), FT-IR and ³¹P{¹H} NMR spectrometry. The spectroscopic studies suggest cis-chelate bidentate coordination of the ligand in fac-[Re(CO)₃Br{R₂P(S)P(S)R₂}] and cis-bridging bidentate coordination of the ligand between two metals in [Re₂(CO)₈Br₂{cis-μ-R₂P(S)P (S)R₂}] (R = Me, Et, ⁿPr, ⁿBu, Ph). An X-ray diffraction study of [ReBr(CO)₃(Et₂P(S)P(S)Et₂)] confirms that the rhenium adopts a distorted octahedral geometry with local C_s symmetry.

Full text of DOI:10.1016/S0277-5387(03)00327-9

Polyhedron 22 (2003) 1659ꢁ1664
/
www.elsevier.com/locate/poly
Photochemical reactions of Re(CO)5Br with tetraalkyldiphosphine
n
Me, Et, Pr, Bu, Ph) and the crystal structure of
n
disulfides (Rꢀ
/
[ReBr(CO)3(Et2P(S)P(S)Et2)]
Ozan Sanl Senturk a,b,*, Hawry A. Shekhel a, Brian T. Sterenberg b,
ı ¸
Konantin A. Udachin , Sema Sert , Ummuhan Ozdemir , Fadime Ug˘ur Sarikahya
¨
¨
b
a
c
a
¨
¨
a Department of Chemistry, Faculty of Science, Ege University, Bomova, 35100 Izmir, Turkey
b Steacie Institute for Molecular Sciences, National Research Council of Canada, 100 Sussex Drive, Ottawa, Ont., Canada K1A 0R6
c Department of Chemistry, Faculty of Science and Literature, Gazi University, Teknikokullar, 06500 Ankara, Turkey
Received 24 August 2002; accepted 15 April 2003
Abstract
The hitherto unknown series of complexes fac-[Re(CO)3Br{R2P(S)P(S)R2}] 1aꢁ
/
5a (1a, Rꢀ
/
Me; 2a, Rꢀ
/
Et; 3a, Rꢀn
Bu; 5b, Rꢀ
/
Pr; 4a,
Rꢀn
/
Bu; 5a, RꢀPh) and [Re2(CO)8Br2{cis-m-R2P(S)P(S)R2}] 1bꢁ5b [1b, RꢀMe; 2b, Rꢀ
/
/
/
/
Et; 3b, Rꢀn
/
Pr; 4b, Rꢀn
/
/
Ph] have been prepared by the photochemical reaction of Re(CO)5Br with R2P(S)P(S)R2. The complexes have been characterized by
elemental analysis, mass spectroscopy (EI), FT-IR and 31P{1H} NMR spectrometry. The spectroscopic studies suggest cis-chelate
bidentate coordination of the ligand in fac-[Re(CO)3Br{R2P(S)P(S)R2}] and cis-bridging bidentate coordination of the ligand
between two metals in [Re2(CO)8Br2{cis-m-R2P(S)P(S)R2}] (Rꢀ
/
Me, Et, nPr, nBu, Ph). An X-ray diffraction study of
[ReBr(CO)3(Et2P(S)P(S)Et2)] confirms that the rhenium adopts a distorted octahedral geometry with local Cs symmetry.
# 2003 Elsevier Science Ltd. All rights reserved.
Keywords: Diphosphine disulfide
1. Introduction
Both product types detailed above the tetraalkyldi-
phosphine disulfides remain intact. This is not always
the case and in certain reactions fragmentation has been
observed. For example, the formation of, inter alia,
[Me2PS2] ions has been reported upon reaction of OH
with Me2P(S)P(S)Me2 in the chemical ionization source
of a mass spectrometer [10]. The reaction of Co2(CO)8
and Me2P(S)P(S)Me2 was first described in 1972 and
two clusters were reported [11], while later the X-ray
crystal structure of one of these, namely [Co4(CO)9(m3-
Since the preparation of the first tetraalkyldipho-
sphine disulfides complexes in 1965 [1ꢁ7] such com-
/
pounds have continued to attract attention, in part
because of the different possible coordination geome-
tries which the ligand may adopt. We have recently
discovered a photochemical reaction of M(CO)6 (Mꢀ
/
n
n
Mo, W) with R2P(S)P(S)R2 (Rꢀ
give the chelate complexes [M(CO)4{R2P(S)P(S)R2}]
(Rꢀ
Me, Et, nPr, nBu) [8], where the ligand is presumed
/
Me, Et, Pr, Bu) to
/
S)(m-PMe2)] confirmed that both phosphorusꢁ
and phosphorusꢁphosphorus scission had occurred
[12,13].
/sulfur
to adopt the expected cis-chelate bidentate coordina-
tion. However, in certain cases, the ligand bridges
/
between
R2P(S)P(S)R2}] (Rꢀ
products.
two
metals
affording
[M2(CO)10{m-
In this paper, we report the preparation and char-
acterization of new complexes fac-[Re(CO)3Br-
{R2P(S)P(S)R2}] and [Re2(CO)8Br2{cis-m-R2P(S)P-
/
Me, Et, nPr, nBu) [9] as secondary
(S)R2}] (Rꢀ
Me, Et, nPr, nBu, Ph), which were pre-
/
pared by photochemical reactions between Re(CO)5Br
with Ph2P(S)P(S)Ph2. The complexes were characterized
by elemental analyses, mass spectroscopy (EI), FT-IR
* Corresponding author. Tel.: ꢂ
E-mail address: ozan.senturk@nrc.ca (O.S. Senturk).
¸
¨
/
1-613-990-5836.
0277-5387/03/$ - see front matter # 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0277-5387(03)00327-9

1660
O.S. Senturk et al. / Polyhedron 22 (2003) 1659ꢁ1664
/
¸
¨
and 31P{1H} NMR spectroscopy. The spectroscopic
studies suggest cis-chelate bidentate coordination of
the ligand in fac-[Re(CO)3Br{R2P(S)P(S)R2}] and cis-
bridging bidentate coordination of the ligand between
dark yellow solid which was washed with petroleum
ether and dried under vacuum, and shown to be fac-
[Re(CO)3Br{Me2P(S)P(S)Me2}] (1a) (42% yield). The
yellow solution was evaporated and the residue sepa-
rated chromatographically through a column packed
with silica gel using n-pentane as an eluant. A yellow
fraction was isolated and dried in vacuo to give
[Re2(CO)8Br2{cis-m-Me2P(S)P(S)Me2}] (1b) (39% yield).
two metals in [Re2(CO)8Br2{cis-m-R2P(S)P(S)R2}] (Rꢀ
/
Me, Et, nPr, nBu, Ph). An X-ray diffraction study of
[ReBr(CO)3(Et2P(S)P(S)Et2)] confirms that the rhenium
adopts a distorted octahedral geometry with local Cs
symmetry.
2.3. 1a
2. Experimental
ReC7H12O3P2S2Br, (MWꢀ536), Calc.: C, 15.7; H,
/
2.3; S, 11.9. Found: C, 15.9; H, 2.7; S, 12.0%. IR (KBr),
n(CO): 2022(s), 1934(s), 1901(s) cmꢃ1; nsym(PS): 580
;
cmꢃ1; nas(PS): 542 cmꢃ1 31P{1H} NMR (100 MHz
2.1. General
Reactions were carried out under dry nitrogen by
using Schlenk techniques. All solvents were dried and
degassed prior to use. Elemental analyses were carried
out using a LECO-CHNS-O-9320 by Technical and
Scientific Research Council of Turkey, TUBITAK. FT-
IR spectra were recorded on samples in hexane at the
Ege University on a Mattson 1000 FT spectrophot-
ometer. 31P{1H} NMR spectra were recorded in CDCl3/
CD2Cl2 at UCL on a BRUKER DPX-400, 400 MHz
High Performance Digital FT-NMR, TUBITAK. Elec-
tron Impact-Mass Spectra were recorded on Micromass
VG Platform-II LC-MS at TUBITAK. UV irradiations
were performed with a medium-pressure 400 W mercury
lamp through a quartz-walled immersion well reactor.
Pentane, benzene, hexane, dichloromethane, acetone
and silica gel were purchased from Merck, and
Re(CO)5Br was purchased from Aldrich. These reagents
were used as supplied. The tetraaalkyldiphosphine
CD2Cl2) dP: 54.7 ppm. MS (EI, 70 eV), m/z (%): 532.63
(6.25), [Mꢂ ꢀ(4H)]; 322 (7.25), [Mꢂ ꢀ
(tmpsꢂCO)]; 294
(12.50), [Mꢂ ꢀ 2CO)]; 266 (40.2), [Mꢂ ꢀ
(tmpsꢂ (tmpsꢂ
3CO)]; 186 (18.06), [Mꢂ ꢀ
(3COꢂBr)].
/
/
/
/
/
/
/
/
/
2.4. 2a
ReC11H20O3P2S2Br, (MWꢀ
3.4; S, 10.8. Found: C, 22.5; H, 3.7; S, 10.9%. IR (KBr),
/592), Calc.: C, 22.3; H,
n(CO): 2019(s), 1919(s), 1898(s) cmꢃ1; nsym(PS): 577
;
cmꢃ1; nas(PS): 535 cmꢃ1 31P{1H} NMR (100 MHz
CD2Cl2) dP: 70.6 ppm. MS (EI, 70 eV), m/z (%): 242.06
(51.67), [Mꢂ ꢀ CO)]; 214.65 (6.07), [Mꢂ ꢀ
(tepsꢂBrꢂ
(tepsꢂBrꢂ (tepsꢂBrꢂ
2CO)]; 186.06 (12.26), [Mꢂ ꢀ
/
/
/
/
/
/
/
/
/
3CO)].
disulfides R2P(S)P(S)R2 (Rꢀ
Me, Et, nPr, nBu, Ph)
were prepared by literature methods [14,15].
/
2.5. 3a
ReC15H28O3P2S2Br, (MWꢀ648), Calc.: C, 27.8; H,
/
2.2. Synthesis
4.4; S, 9.9. Found: C, 28.0; H, 4.6; S, 10.1%. IR (KBr),
n(CO): 2018(s), 1912(s), 1893(s) cmꢃ1; nsym(PS): 595
The complexes, fac-[Re(CO)3Br{R2P(S)P(S)R2}], 1aꢁ
5a, and [Re2(CO)8Br2{cis-m-R2P(S)P(S)R2}], 1bꢁ5b,
were prepared by the photochemical reactions of
Re(CO)5Br with R2P(S)P(S)R2 (Rꢀ
Me, Et, nPr, nBu,
Ph) and obtained in 40ꢁ60% yield by similar methods of
/
cmꢃ1; nas(PS): 562 cmꢃ1 31P{1H} NMR (100 MHz
;
/
CD2Cl2) dP: 66.9 ppm. MS (EI, 70 eV), m/z (%): 540 (6),
[Mꢂ ꢀ
(COꢂBr)]; 149 (100), [Pr2P(S)]; 106 (85), [PrP(S)];
63 (45), [P(S)]; 512 (10), [Mꢂ ꢀ
(2COꢂBr)]; 484 (6),
[Mꢂ ꢀ
(3COꢂBr)].
/
/
/
/
/
/
/
/
which the following is typical.
The complexes Re(CO)5Br (0.8 g, 2 mmol) and
Me2P(S)P(S)Me2 (0.18 g, 1 mmol) were dissolved in
2.6. 4a
ReC19H36O3P2S2Br, (MWꢀ648), Calc.: C, 32.4; H,
5.2; S, 9.1. Found: C, 32.7; H, 5.3; S, 9.2%. IR (KBr),
tetrahydrofuran (80ꢁ100 ml) and the solution was
/
irradiated for 2 h using a 400-W medium-pressure
mercury lamp through a quartz-walled immersion well
reactor. During the irradiation, the colour of the
solution changed from colourless to dark yellow. After
the irradiation the solvent was evaporated under the
vacuum resulting in a dark yellow solid which was
extracted into dichloromethane (10 ml). Addition of
petroleum ether (50 ml) resulted in precipitation of a
/
n(CO): 2016(s), 1911(s), 1891(s) cmꢃ1; nsym(PS): 592
cmꢃ1; nas(PS): 565 cmꢃ1 31P{1H} NMR (100 MHz
;
CD2Cl2) dP: 67.3 ppm. MS (EI, 70 eV), m/z (%): 647 (5),
[Mꢂ ꢀBu]; 533 (20), [Mꢂ ꢀ3Bu]; 476 (5), [Mꢂ ꢀ
4Bu];
420 (4), [Mꢂ ꢀ 2CO)]; 392 (4), [Mꢂ ꢀ
(4Buꢂ (4Buꢂ
3CO)]; 266 (13.74), [Mꢂ ꢀ
(tbpsꢂCO)].
/
/
/
/
/
/
/
/
/

O.S. Senturk et al. / Polyhedron 22 (2003) 1659ꢁ
/
1664
1661
¸
¨
2.7. 5a
ReC27H20O3P2S2Br, (MWꢀ
2.6; S, 8.2. Found: C, 41.8; H, 2.9; S, 8.3%. IR (KBr),
Br(CO)4ꢂ
/
Buꢂ
/
Sꢂ
/
3CO)];
531
(15),
[Mꢂ ꢀ
/
Re-
Br(CO)4ꢂBuꢂ
/
/
Sꢂ
/4CO)].
/
648), Calc.: C, 41.3; H,
2.12. 5b
ReC32H20O8P2S2Br, (MWꢀ1190), Calc.: C, 32.3; H,
1.7; S, 5.4. Found: C, 32.5; H, 1.9; S, 5.6%. IR (KBr),
n(CO) 2102(vs), 2015(s), 1933(s), 1908(s) cmꢃ1; nsym(PS)
613 cmꢃ1; nas(PS) 571 cmꢃ1 31P{1H} NMR (100 MHz
;
n(CO): 2014(s), 1905(s), 1890(s) cmꢃ1; nsym(PS): 601
cmꢃ1; nas(PS): 582 cmꢃ1
;
31P{1H} NMR (100 MHz
/
CD2Cl2) dP: 63.5 ppm. MS (EI, 70 eV), m/z (%): 350 (8),
[Mꢂ ꢀtPhps]; 322 (5), [Mꢂ ꢀ
(COꢂtPhps)]; 294 (10),
[Mꢂ ꢀ tPhps)]; 266 (20), [Mꢂ ꢀ
(2COꢂ (3COꢂtPhps)];
186 (6.5), [Mꢂ ꢀ
(3COꢂtPhpsꢂBr)].
/
/
/
/
/
/
/
/
/
/
CD2Cl2) dP: 84.3 ppm. MS (EI, 70 eV), m/z (%): 490
(90), [Mꢂ ꢀ
(ReBr(CO)4(Ph)2PS)ꢂPhꢂCO)]; 462 (30),
[Mꢂ ꢀ
(ReBr(CO)4(Ph)2PS)ꢂPhꢂ2CO)]; 434 (30),
[Mꢂ ꢀ
((ReBr(CO)4(Ph)2PS)ꢂPhꢂ3CO)].
/
/
/
2.8. 1b
/
/
/
/
/
/
ReC12H12O8P2S2Br, (MWꢀ
1.8; S, 6.8. Found: C, 15.5; H, 1.6; S, 6.5%. IR (KBr),
n(CO): 2100(vs), 2011(s), 1922(s), 1899(s) cmꢃ1
nsym(PS): 588 cmꢃ1; nas(PS): 539 cmꢃ1 31P{1H} NMR
(100 MHz CD2Cl2) dP: 94.1 ppm. MS (EI, 70 eV), m/z
(%): 521 (40), [Mꢂ ꢀ
(ReBr(CO)4ꢂMeꢂCO)]; 493 (25),
[Mꢂ ꢀ 2CO)]; 465 (20), [Mꢂ ꢀ
(ReBr(CO)4ꢂMeꢂ (Re-
Br(CO)4ꢂMeꢂ (ReBr(CO)4ꢂ
3CO)]; 437 (100), [Mꢂ ꢀ
Meꢂ4CO)].
/942), Calc.: C, 15.9; H,
For the mass spectral data relative intensities are
given in parentheses; probable assignments in square
brackets. For all assignments the most abundant
isotopes of Re has been selected (187Re, 62.9% abun-
dant).
;
;
/
/
/
/
/
/
/
2.13. Crystallography
/
/
/
/
/
A single crystal of 2a was mounted on a glass fibre.
Diffraction measurements were made on a Siemens
SMART CCD automatic diffractometer using gra-
phite-monochromated Mo Ka radiation. The unit cell
was determined from randomly selected reflections
obtained using the SMART CCD automatic search,
center index and least-squares routines. Crystal data and
collection parameters are listed in Table 1. Integration
was carried out using the program SAINT and an
2.9. 2b
ReC16H20O8P2S2Br, (MWꢀ
2.0; S, 6.4. Found: C, 19.9; H, 2.3; S, 6.9%. IR (KBr),
n(CO): 2101(vs), 2004(s), 1933(s), 1905(s) cmꢃ1
nsym(PS): 564 cmꢃ1; nas(PS): 524 cmꢃ1 31P{1H} NMR
(100 MHz CD2Cl2) dP: 91.1 ppm. MS (EI, 70 eV), m/z
(%): 413 (10), [Mꢂ ꢀ
(ReBr(CO)4 (Et)2 PS)ꢂ2EtꢂCO)];
385 (20), [Mꢂ ꢀ
(ReBr(CO)4 (Et)2PS)ꢂ2Etꢂ2CO)]; 357
(20) [Mꢂ ꢀ
(ReBr (CO)4(Et)2 PS)ꢂ2Etꢂ3CO)]; 329 (25),
[Mꢂ ꢀ
(ReBr(CO)4(Et)2PS)ꢂ2Etꢂ4CO)].
/998), Calc.: C, 19.2; H,
;
;
/
/
/
absorption correction was performed using SADABS.
/
/
/
Structure solution was carried out using the SHELXTL
5.1 suite of programs. The space group P21/n was
chosen based upon systematic absences. The initial
solution was obtained by direct methods and refined
by successive least-squares cycles.
/
/
/
/
/
/
2.10. 3b
ReC20H28O8P2S2Br, (MWꢀ
2.7; S, 6.1. Found: C, 22.5; H, 2.9; S, 5.9%. IR (KBr),
n(CO): 2098(vs), 2015(s), 1932(s), 1898(s) cmꢃ1
nsym(PS): 589 cmꢃ1; nas(PS): 548 cmꢃ1 31P{1H} NMR
(100 MHz CD2Cl2) dP: 87.3 ppm. MS (EI, 70 eV), m/z
(%): 530 (30), [Mꢂ ꢀ
(ReBr(CO)4ꢂ2PrꢂSꢂCO)]; 502
(16), [Mꢂ ꢀ
(ReBr(CO)4ꢂ2PrꢂSꢂ2CO)]; 474 (10),
[Mꢂ ꢀ 3CO)]; 446 (100), [Mꢂ ꢀ
(ReBr(CO)4ꢂ2PrꢂSꢂ
(ReBr(CO)4ꢂ2PrꢂSꢂ4CO)].
/
1054), Calc.: C, 22.8; H,
3. Result and discussion
;
;
The photogeneration of M(CO)5 from M(CO)6 (Mꢀ
/
Cr, Mo or W) has been extensively studied. These 16-
electron M(CO)5 fragments react avidly with any
available donor to form M(CO)5L species, and where
L is a chelating bidentate ligand, rapid continuation to
the chelating M(CO)4L or bridging M2(CO)10(m-L)
products may occur [8,9,16]. The photochemical reac-
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
2.11. 4b
ReC24H36O8P2S2Br, (MWꢀ
3.3; S, 5.8. Found: C, 25.7; H, 3.5; S, 5.4%. IR (KBr),
tions of Re(CO)5Br with R2P(S)P(S)R2 (Rꢀ
/
Me, Et,
nPr, Bu, Ph) proceed in this expected manner to yield
the hitherto unknown series of complexes 1aꢁ5a and
1bꢁ5b.
The IR spectra data for 1aꢁ
n
/
1010), Calc.: C, 25.9; H,
/
/
n(CO) 2102(vs), 2010(s), 1929(s), 1897(s) cmꢃ1; nsym(PS)
/
5a and 1bꢁ5b show a
/
590 cmꢃ1; nas(PS) 549 cmꢃ1
;
31P{1H} NMR (100 MHz
decrease in nas(PS) on coordination. In the free ligand
the IR active mode nas(PS) is at 569 cmꢃ1 for
tetramethyldiphosphine disulfide [8,9,17]. On cis-chelate
coordination two bands are observed: at ca. 580 cmꢃ1
CD2Cl2) dP: 88.2 ppm. MS (EI, 70 eV), m/z (%): 615
(10), [Mꢂ ꢀ CO)]; 587 (10), [Mꢂ ꢀ
(ReBr(CO)4ꢂBuꢂSꢂ
ReBr(CO)4ꢂBuꢂSꢂ Re-
2CO)]; 559 (15), [Mꢂ ꢀ
/
/
/
/
/
/
/
/
/

1662
O.S. Senturk et al. / Polyhedron 22 (2003) 1659ꢁ1664
/
¸
¨
Table 1
Crystal data and structure refinement of 2a
lower wave numbers when compared with the starting
Re(CO)5Br molecules [8,9] (Fig. 1).
The 31P{1H} NMR spectra of complexes, 1aꢁ
/5a and
Empirical formula
Formula weight
Temperature (K)
C11H20BrO3P2ReS2
592.44
173(2)
1bꢁ/5b, show one signal corresponding to the phospho-
rus atoms of the coordinated ligands. The dP values of
the coordinated ligands are at higher field than those of
free ligands and the coordinated cis-bridging ligands are
also at higher field than when the ligands are coordi-
nated in a cis-chelating mode. Only one signal is
observed in accord with the symmetry of the complexes
[8,9,18].
The mass spectra show fragmentation via successive
loss of CO groups and fragmentation of the organic
ligands.
Single crystals of [ReBr(CO)3(Et2P(S)P(S)Et2)] (2a),
were grown by slow diffusion of hexanes into a CH2Cl2
solution and an ORTEP diagram of the molecule is shown
in Fig. 2 and selected bond lengths and angles are given
in Table 2. X-ray diffraction of 2a shows that the
tetraethyldiphosphine disulfides group adopts a chelat-
ing bidentate mode of ligation. The sulfur atoms of the
tetraethyldiphosphine disulfides are bonded trans to CO
groups, with the remaining CO group and the Br group
occupying axial sites. The rhenium atom is thus six-
coordinate with a somewhat distorted octahedral ar-
˚
Wavelength (A)
0.71073
monoclinic
P21/n
Crystal system
Space group
Unit cell dimensions
˚
a (A)
9.2966(9)
19.221(2)
10.637(1)
90.00
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
104.125(2)
90.00
3
˚
V (A )
1843.2(3)
4
2.135
Z
Dcalc (Mg mꢃ3
Absorption coefficient (mmꢃ1
F(0 0 0)
)
)
9.162
1128
u Range for data collection (8)
Limiting indices
2.12ꢁ
125
145
/
28.74
h 5
l 514
ꢃ
ꢃ/
/
/
/
12, ꢃ
/
265
/
k 525,
/
/
/
Reflections collected
Independent reflections
Completeness to u
21526
4767
99.5
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
full-matrix least-squares on F2
4767/0/181
1.067
Final R indices [I ꢀ
R indices (all data)
Largest difference peak and hole
/
2s(I)]
R1ꢀ
R1ꢀ
6.276 and ꢃ
/
0.0642, wR2ꢀ
0.0510, wR2ꢀ
3.275
/
0.1342
rangement of the coordinating atoms. The Reꢀ
/
S
S (1.996(2) and
/
/0.1251
˚
(2.555(2) and 2.6154(8) A) and Pꢀ
/
/
˚
1.990(2) A) distance are in line with those observed for
ꢃ3
˚
(e A
)
related complexes. For example, in the molecules
[Re(CO)3(Et4-DTO)Br] (A), and [ReNCl{N(SPPh2)2-
nsym(PS) and ca. 542 cmꢃ1 nas(PS), e.g. in
[Re(CO)3Br{Me2P(S)P(S)Me2}] (1a). On cis-bridging
coordination two bands are observed: at ca. 588 cmꢃ1
nsym(PS) and ca. 539 cmꢃ1 nas(PS) e.g. in
[Re2(CO)8Br2{cis-m-Me2P(S)P(S)Me2}] (1b). The infra-
red spectra of the [Re(CO)3BrL-L] compounds are
S,S?}(PPh3)] (B), the average Reꢀ
[25,26] and in the molecule
D)(Et2P(S)P(S)Et2]ClO4 (C), the average Pꢀ
/
S distance 2.473 A
˚
[Rh(CO-
S distance
sulfur and
/
˚
2.001 A [18]. The somewhat longer metalꢁ
rather shorter Pꢀ
somewhat weaker coordination of the sulfur ligand in
2a. The PꢀS distances in 2a are intermediate between
those associated with formal single (2.122(1) A) [20] and
/
/
S distances in 2a presumably reflect
/
consistent with a structure in which Lꢀ
/
L are cis to the
˚
Br as well as to each other. The infrared spectra for the
complexes contain three strong carbonyl bands allowing
˚
1.966(2) A) phosphorus sulfur
bonds [21]. This finding suggests some of the delocaliza-
double (range 1.923(5)ꢁ
/
an unequivocal assignment of [Re(CO)3BrLꢀ
/L] com-
tion of electrons and observed that the two Pꢀ
/
S
distances in 2a are identical within the limits of
pounds as the fac-isomer of Cs symmetry. The symme-
try of these complexes fac-[Re(CO)3Br{R2P(S)-
experimental uncertainty [24].
P(S)R2}](Rꢀ
Me, Et, nPr, nBu, Ph) is Cs. The three
carbonyl stretching vibrations being distributed
/
The lengthening of the Pꢀ
/
S bond upon coordination
˚
from the value observed in the free ligand (v. 1.94(1) A)
[22] is probably due to the lower electronic density
available at the sulfur atom after its coordination to the
metal center, and is reflected at the sulfur atom after its
coordination to the metal center, and is reflected in the
amongst the symmetry classes of the point group as
follows (tꢀ
[Re2(CO)8Br2{cis-m-Lꢀ
with a structure in which Lꢀ
expected, four bands arising from n(CO) vibrations are
seen for each complex 1bꢁ5b which presumably have
local C2v symmetry of the M(CO)4 unit in
/
2Aƒꢂ
/
A?) [19]. The infrared spectra of the
L}] compounds are consistent
L are cis to the Br. As
/
/
decrease in the decrease in the (Pꢀ
the region 580ꢁ
530 cmꢃ1
On the other hand, no significant change is observed
/S) IR band found in
/
/
.
[Re2(CO)8Br2{cis-m-R2P(S)P(S)R2}](Rꢀ
/
Me, Et, nPr,
˚
P bond separation (2.213(2) A) when com-
pared with the value reported for the free tetraethyldi-
for the Pꢀ
/
nBu, Ph). The IR spectroscopic results are in accord
with a cis-chelating and a cis-bridging coordination
˚
phosphine disulfides Et2P(S)(S)PEt2 (2.22(1) A) [22].
Probably this bond is too far away from the metal to
ligand. The n(CO) modes of 1aꢁ
/
5a and 1bꢁ
/
5b move to

O.S. Senturk et al. / Polyhedron 22 (2003) 1659ꢁ
/
1664
1663
¸
¨
Fig. 1. The photochemical reactions of Re(CO)5Br with R2P(S)P(S)R2 (Rꢀ
Me, Et, n Pr, n Bu, Ph).
/
In addition, the values for the Reꢀ
/
Sꢀ/P angles
(102.56(8) and 105.17(8) (8)), close to tetrahedral,
indicates formal sp3 hybridization for sulfur, as reported
for the related rhodium compound C [19]. These facts
support the suggestion, that the phosphineꢁsulfides can
/
be regarded as moderate s-donor ligands with minimal
p-acceptor properties [23].
We have presented the novel photochemical reactions
between Re(CO)5Br and R2P(S)(P(S)R2 (Rꢀ
nPr, nBu, Ph). The IR spectroscopic results are in accord
with a cis-chelating 1aꢁ5a and a cis-bridging 1bꢁ5b
bidentate coordination of the ligand [3]. The n(CO)
modes of 1bꢁ5b move to low wavenumber when
/Me, Et,
/
/
/
compared with the starting Re(CO)5Br molecules. The
31P NMR data show that the P atoms of the R4P2S2
ligands are somewhat deshielded with respect to the free
ligand. The mass spectrum shows fragmentation via
successive loss of CO groups and fragmentation of the
R2P(S)P(S)R2 ligand. In addition, the spectroscopic
study of 2a is entirely keeping with the single crystal
X-ray diffraction study.
Fig. 2. Molecular structure of [ReBr(CO)3(Et2P(S)P(S)Et2)] (2a).
Thermal ellipsoids are shown at the 50% probability level and
hydrogen atoms have been ommitted.
interact any appreciable modification upon coordina-
tion.
Table 2
˚
4. Supplementary material
Selected bond lengths (A) and angles (8) for 2a
Bond lengths
A complete list of bond lengths and angles and tables
of atomic coordinates and thermal parameters have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC No. 190232. Copies of this
information may be obtained free of charge from the
Director, CCDC, 12 Union Road, Cambridge, CB2
Reꢀ
Reꢀ
Reꢀ
/
C(1)
C(2)
C(3)
1.908(7)
1.906(7)
1.881(7)
1.996(2)
1.990(2)
Reꢀ
Reꢀ
Reꢀ
/
S(1)
S(2)
Br
2.561(2)
2.555(2)
2.6514(8)
2.213(2)
/
/
/
/
S(1)ꢀ
/
P(1)
P(2)
P(1)ꢀP(2)
/
S(2)ꢀ
/
Bond angles
C(3)ꢀReꢀ
C(3)ꢀReꢀ
C(2)ꢀReꢀ
C(3)ꢀReꢀ
C(2)ꢀReꢀ
C(1)ꢀReꢀ
C(3)ꢀReꢀ
C(2)ꢀReꢀ
C(1)ꢀReꢀ
/
/
C(2)
C(1)
C(1)
S(2)
S(2)
S(2)
S(1)
S(1)
S(1)
88.0(3)
89.7(3)
91.0(3)
91.8(2)
174.7(2)
83.8(2)
93.0(2)
92.3(2)
175.8(2)
S(2)ꢀ
C(1)ꢀ
C(3)ꢀ
C(2)ꢀ
S(1)ꢀReꢀ
S(2)ꢀReꢀ
S(1)ꢀ
S(2)ꢀ
/
Reꢀ
Reꢀ
Reꢀ
Reꢀ
/
S(1)
92.92(5)
90.6(2)
1EZ, UK (fax: ꢂ44-1223-336033; e-mail: deposit@
/
/
/
/
/
Br
Br
Br
ccdc.cam.ac.uk or www http://www.ccdc.cam.ac.uk).
/
/
/
/
177.2(2)
89.2(2)
/
/
/
/
/
/
/
/
Br
86.85(4)
90.96(5)
102.56(8)
105.17(8)
/
/
/
/
Br
Acknowledgements
/
/
/
P(1)ꢀ
P(2)ꢀ
/Re
/
/
/
/Re
We thank BP (Turkey) for the provision of photo-
chemical apparatus and Research Foundation of Ege
/
/

1664
O.S. Senturk et al. / Polyhedron 22 (2003) 1659ꢁ1664
/
¸
¨
Longman, London, 1977, pp. 139ꢁ
/
145, 163ꢁ
/
179, 193, 280ꢁ288.;
/
University for funds. We thank TUBITAK for alloca-
tion of time at the NMR, Mass Spectra and Elemental
Analyses. We thank Dr. Arthur J. Carty for allowing
use of the X-ray facilities at the National Research
Council of Canada.
(d) H. Nierbergall, B. Langenfeld, Chem. Ber. 95 (1962) 64.
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