Reactivity of phenyldi(2-thienyl)phosphine towards group 7 metal carbonyls: Carbon-phosphorus bond activation

Article abstract of DOI:10.1016/j.ica.2009.09.021

Addition of phenyldi(2-thienyl)phosphine (PPhTh₂) to Re₂(CO)_10-n(NCMe)_n (n = 1, 2) affords the substitution products Re₂(CO)_10-n(PhPTh₂) _n (1, 2) together with small a

Full text of DOI:10.1016/j.ica.2009.09.021

Inorganica Chimica Acta 362 (2009) 5175–5182
Contents lists available at ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Reactivity of phenyldi(2-thienyl)phosphine towards group 7 metal carbonyls:
Carbon–phosphorus bond activation
Shishir Ghosh a, Alok K. Das a, Noorjahan Begum b, Daniel T. Haworth c, Sergey V. Lindeman c,
James F. Gardinier c, Tasneem A. Siddiquee d, Dennis W. Bennett d, Ebbe Nordlander b,
,
*
Graeme Hogarth e, Shariff E. Kabir a,
*
a Department of Chemistry, Jahangirnagar University, Savar, Dhaka-1342, Bangladesh
b Inorganic Chemistry Research Group, Chemical Physics, Center for Chemistry and Chemical Engineering, Lund University, P. O. Box 124, SE-22100 Lund, Sweden
c Department of Chemistry, Marquette University, P. O. Box 1881, Milwaukee, Wisconsin 53201-1881, USA
d Department of Chemistry, University of Wisconsin-Milwaukee, P. O. Box 413, Milwaukee, Wisconsin 53211-3029, USA
e Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK
a r t i c l e i n f o
a b s t r a c t
Article history:
Addition of phenyldi(2-thienyl)phosphine (PPhTh2) to [Re2(CO)10Àn(NCMe)n] (n = 1, 2) affords the substi-
tution products [Re2(CO)10Àn(PhPTh2)n] (1, 2) together with small amounts of fac-[ClRe(CO)3(PPhTh2)2]
(3) (n = 2). Reaction of [Re2(CO)10] with PPhTh2 in refluxing xylene affords a mixture which includes 2,
Received 7 August 2009
Accepted 4 September 2009
Available online 13 September 2009
[Re2(CO)7(PPhTh2)(l-PPhTh)(l-H)] (4), [Re2(CO)7(PPhTh2)(l-PPhTh)(l- ,j
g1 1(S)-C4H3S)] (5) and mer-
[HRe(CO)3(PPhTh2)2] (6). Phosphido-bridged 4 and 5 are formed by the carbon–phosphorus bond cleav-
age of the coordinated PPhTh2 ligand, the cleaved thienyl group being retained in the latter. Reaction of
[Mn2(CO)10] with PPhTh2 in refluxing toluene affords [Mn2(CO)9(PPhTh2)] (7) and the carbon–phospho-
Keywords:
Rhenium carbonyl
Manganese carbonyl
Phenyldi(2-thienyl)phosphine
Carbon–phosphorus bond cleavage
X-ray structures
rus bond cleavage products [Mn2(CO)6(
PPhTh)(
5-C4H3S)] (9). Both 8 and 9 contain a bridging thienyl ligand which is bonded to one man-
ganese atom in a
5-fashion.
l-PPhTh)(l- ,g l-
g1 5-C4H3S)] (8) and [Mn2(CO)5(PPhTh2)(
l- ,g
g1
g
Ó 2009 Elsevier B.V. All rights reserved.
1. Introduction
been observed. For example, we have recently shown that carbon–
sulfur bond scission of a coordinated PTh3 ligand at a triruthenium
The coordination chemistry of thiophene and its derivatives
with transition metal complexes has been extensively explored
to understand the nature of the important reactions involved in
metal-catalyzed hydrodesulfurization (HDS), a process that re-
moves sulfur from the organosulfur impurities that are commonly
found in liquid fuels [1–16]. Numerous examples of thiophene
coordination and activation have demonstrated that thiophene
and its benzo-derivatives are not useful as ligands for transition
metals, even for soft metals that normally bind strongly to sulfur.
To overcome this disadvantage, thienyl phosphines have been used
to introduce the heterocycle into the metal coordination sphere
[17–25].
center leads to the formation of a l3-g
3-1-thia-butadiene ligand
[26]. In contrast, the reactivity of group 7 metal carbonyls with thi-
enyl phosphines has not been as extensively studied. Deeming
et al. have investigated the reactivity of Ph2PTh with [Re2(CO)10
and [Mn2(CO)10] [25] which leads to a number of interesting prod-
ucts (Chart 1). The dirhenium complex [Re2(CO)8(
]
l- , -
j1 j1
Ph2PC4H3S)] (A) results from the photochemical reaction with
[Re2(CO)10], whilein refluxingxylene theisomericcarbon–phospho-
rus bond cleavage product [Re2(CO)8(l-PPh2)(l- :j
g1 1(S)-C4H3S)]
(B) results. With [Mn2(CO)10] the reaction proceeds differently and
in refluxing xylene a mixture of [Mn2(CO)9(Ph2PTh)] (C) and
[Mn2(CO)6(l-PPh2)(l- :g
g1 5-C4H3S)] (D) are obtained. We recently
The reactivity of metal carbonyls of the iron triad with thienyl
phosphines such as Ph2PTh (Th = 2-thienyl) [18–21], PhPTh2 [22],
diphenyl(benzothienyl)phosphine [22] and PTh3 [23,24] is well-
documented, and a wealth of intriguing reactivity patterns have
reported the reactivity of PTh3 with the lightly stabilized dirhenium
complexes [Re2(CO)10Àn(NCMe)n] (n = 0, 1, 2) and [Mn2(CO)10] [27].
With rhenium carbonyls,
a series of mono- and dirhenium
complexes were obtained (E–M, Chart 2) while with [Mn2(CO)10
]
products N–P (Chart 2) are similar to those reported with
Ph2PTh. For comparison, we have now investigated the reactivity
of PhPTh2 with group 7 metal carbonyls, details of which are re-
ported herein.
* Corresponding authors.
E-mail address: skabir_ju@yahoo.com (S.E. Kabir).
0020-1693/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2009.09.021

5176
S. Ghosh et al. / Inorganica Chimica Acta 362 (2009) 5175–5182
25 °C for 90 h. The solvent was removed by rotary evaporation
and the residue separated by TLC on silica gel. Elution with hex-
ane/CH2Cl2 (7:3, v/v) developed three bands. The first and second
bands gave unreacted [Re2(CO)10] (trace) and PPhTh2 (trace),
respectively, while the third band afforded [Re2(CO)9(PPhTh2)]
(1) (116 mg, 84%) as pale yellow crystals after recrystallization
from hexane/CH2Cl2 at 4 °C. Spectral data for 1: Anal. Calc. for
C23H11O9PRe2S2: C, 30.73; H, 1.23. Found: C, 30.96; H, 1.30%. IR
S
S
Ph2P
4 Re
(OC)4 Re
Re(CO)4
(OC)
Re(CO)4
P
Ph2
(A)
(B)
S
(m ;
CO, CH2Cl2): 2110 s, 2039 sh, 2009 vs, 1947 s cmÀ1 1H NMR
(CDCl3): d 7.72 (m, 4H), 7.58 (m, 2H), 7.48 (m, 3H), 7.23 (m, 2H);
(CO)4
Mn
31P-{1H} NMR (CDCl3): d À15.6 (s); MS (FAB): m/z 898 (M+).
(OC)
Mn(CO)2
4 Mn
(OC)5Mn
PPh2Th
P
Ph2
2.2. Reaction of [Re2(CO)8(NCMe)2] with PPhTh2
(C)
(D)
To a CH2Cl2 solution (30 mL) of [Re2(CO)8(NCMe)2] (100 mg,
0.147 mmol), PPhTh2 (81 mg, 0.295 mmol) was added and the
reaction mixture was stirred at 25 °C for 72 h. The solvent was re-
moved under reduced pressure and the resultant residue was sub-
jected to TLC on silica gel. Elution with hexane/CH2Cl2 (7:3, v/v)
developed four bands. The first and second bands gave unreacted
[Re2(CO)8(NCMe)2] (trace) and PPhTh2 (trace), respectively. The
third band afforded [Re2(CO)8(PPhTh2)2] (2) (112 mg, 66%) as yel-
low crystals while the fourth band gave fac-[ClRe(CO)3(PPhTh2)2]
(3) (27 mg, 21%) after recrystallization from hexane/CH2Cl2 at
4 °C. Spectral data for 2: Anal. Calc. for C36H22O8P2Re2S4: C,
Chart 1.
2. Experimental
[Re2(CO)10 and [Mn2(CO)10
]
] were purchased from Strem
Chemicals Inc. and used without further purification, and
[Re2(CO)9(NCMe)] and [Re2(CO)8(NCMe)2] were prepared accord-
ing to published procedures [28]. Phenyldi(2-thienyl)phosphine
(PPhTh2) was purchased from E. Merck and used as received. All
reactions were carried out under a nitrogen atmosphere using
standard Schlenk techniques. Reagent grade solvents were dried
by the standard procedures and were freshly distilled prior to
use. Infrared spectra were recorded on a Shimadzu FTIR 8101 spec-
trophotometer. NMR spectra were recorded on Bruker DPX 400
and Varian Inova 500 instruments. Elemental analyses were per-
formed by Microanalytical Laboratories, University College Lon-
don. Fast atom bombardment mass spectra were obtained on a
JEOL SX-102 spectrometer using 3-nitrobenzyl alcohol as matrix
and CsI as calibrant.
37.76; H, 1.94. Found: C, 38.03; H, 1.99%. IR (
m
CO, CH2Cl2): 2016
w, 1990 sh, 1961 vs cmÀ1
;
1H NMR (CDCl3): d 7.64 (m, 4H), 7.43
(m, 10H), 7.36 (m, 4H), 7.22 (m, 4H); 31P-{1H} NMR (CDCl3): d
À11.6 (s); MS (FAB): m/z 1146 (M+). Spectral data for 3: Anal. Calc.
for C31H22ClO3P2ReS4: C, 43.58; H, 2.60. Found: C, 43.91; H, 2.66%.
IR (m
CO, CH2Cl2): 2039 s, 1960 m, 1907 m cmÀ1; 1H NMR (CDCl3): d
7.56 (m, 4H), 7.49 (m, 4H), 7.33 (m, 7H), 7.23 (m, 3H), 7.03 (m, 4H);
31P-{1H} NMR (CDCl3): d À15.1 (s); MS (FAB): m/z 854 (M+).
2.1. Reaction of [Re2(CO)9(NCMe)] with PPhTh2
2.3. Reaction of [Re2(CO)10] with PPhTh2
A
CH2Cl2 solution (30 mL) of [Re2(CO)9(NCMe)] (100 mg,
A xylene solution (30 mL) of [Re2(CO)10] (200 mg, 0.307 mmol)
and PPhTh2 (168 mg, 0.612 mmol) was heated to reflux for 7 h. The
0.150 mmol) and PPhTh2 (42 mg, 0.153 mmol) was stirred at
NCMe
Th3P
Re
Re
PTh3
Th3P
Re
Re
CO
Th3P
Re
Re
CO
(CO)4
(CO)4
(CO)4
(CO)4
(CO)4
(CO)4
(G)
(E)
S
(F)
Th2
P
S
PTh3
(CO)
(CO)
4 Re
(CO)4Re
Re (CO)4
3Re
Re (CO)4
Re (CO)3
P
H
P
Th3P
Th2
Th2
(J)
(H)
(I)
H
H
S
CO
PTh3
CO
PTh3
(CO)3
Re
OC
OC
Re
Re
(CO)4
Re
Th3P
OC
PTh2
P
Th2
CO
(L)
S
CO
(M)
S
S
(K)
Th3P
(CO)4
Mn
Mn (CO)2
Mn (CO)2
Mn
(OC)
5 Mn
(OC)4Mn
PTh3
(CO)3
P
P
Th2
Th2
(N)
(P)
(O)
Chart 2.

S. Ghosh et al. / Inorganica Chimica Acta 362 (2009) 5175–5182
5177
solvent was removed under reduced pressure and the residue sep-
2.6. X-ray crystallographic studies
arated by TLC on silica gel. Elution with hexane/CH2Cl2 (7:3, v/v)
developed nine bands. The first and second bands gave unreacted
[Re2(CO)10] (trace) and PPhTh2 (trace), respectively. The fifth to
eighth bands afforded the following compounds in order of elu-
Single crystals of compounds 3, 4, 6, 8 and 9 suitable for X-ray
diffraction were obtained by recrystallization from hexane/CH2Cl2
at room temperature and mounted on Nylon fibers with a mineral
oil, and diffraction data were collected at 100(2) K on a Bruker AXS
SMART diffractometer equipped with an APEX CCD detector using
tion: [Re2(CO)7(PPhTh2)(
l
-PPhTh)(
l
-H)] (4) (96 mg, 30%) as color-
less crystals, [Re2(CO)7(PPhTh2)(
l-PPhTh)(
l- ,j
g1
1(S)-C4H3S)] (5)
(64 mg, 19%) as pale yellow crystals, mer-[HRe(CO)3(PPhTh2)2] (6)
(43 mg, 17%) as colorless crystals and 2 (47 mg, 13%) after recrys-
tallization from hexane/CH2Cl2 at 4 °C. The remaining bands gave
minor unidentified products. Spectral data for 4: Anal. Calc. for
C31H20O7P2Re2S3: C, 35.97; H, 1.95. Found: C, 36.32; H, 2.03%. IR
graphite-monochromated Cu Ka radiation (k = 1.54178 Å). Integra-
tion of intensities and data reduction was performed using the SAINT
program [29]. Numerical (based on the real shape of the crystals)
absorption correction was applied in all cases followed by the mul-
ti-scan SADABS procedure [30]. The structures were solved by direct
methods [31] and refined by full-matrix least-squares on F2 [32].
All non-hydrogen atoms were refined anisotropically. Pertinent
crystallographic data and structure refinement parameters are
summarized in Table 1.
(m ;
CO, CH2Cl2): 2094 m, 2048 m, 1998 vs, 1950 s, 1924 s cmÀ1 1H
NMR (CDCl3): d 7.95 (m, 2H), 7.71 (m, 2H), 7.53–7.23 (m, 14H),
7.00 (m, 1H), À13.85 (dd, J = 16.4, 4.8 Hz, 1H); 31P-{1H} NMR
(CDCl3): d 24.1 (d, J = 70.4 Hz, 1P), À18.4 (d, J = 70.4 Hz, 1P); MS
(FAB): m/z 1034 (M+). Spectral data for 5: Anal. Calc. for
C35H22O7P2Re2S4: C, 37.63; H, 1.98. Found: C, 37.98; H, 2.07%. IR
3. Results and discussion
(m
CO, CH2Cl2): 2082 m, 2054 m, 1986 vs, 1974 vs, 1961 vs,
1937 s cmÀ1 1H NMR (CDCl3): d 7.66 (m, 3H), 7.47 (m, 5H), 7.39
;
3.1. Reactions of [Re2(CO)10Àn(NCMe)n] (n = 1,2) with PhPTh2:
substitution products
(m, 3H), 7.22 (m, 5H), 7.06 (m, 4H), 6.90 (m, 1H), 6.38 (m, 1H);
31P-{1H} NMR (CDCl3): d À21.0 (d, J = 98.0 Hz, 1P), À55.9 (d,
J = 98.0 Hz, 1P); MS (FAB): m/z 1118 (M+). Spectral data for 6: Anal.
Calc. for C31H23O3P2ReS4: C, 45.41; H, 2.83. Found: C, 45.73; H,
Treatment of [Re2(CO)9(NCMe)] with PPhTh2 at 25 °C afforded
the substitution product [Re2(CO)9(PPhTh2)] (1) (84%), while
[Re2(CO)8(NCMe)2] similarly gave [Re2(CO)8(PPhTh2)2] (2) (66%).
Both are readily characterized by comparison of spectroscopic data
with related [Re2(CO)10Àn(L)n] complexes (n = 1,2: L = PPh3, PMe3,
PTh3, PFu3) [27,28b,33]. In the 31P-{1H} NMR spectra, both display
only a singlet, at d À15.6 for 1 and À11.6 for 2, suggesting that
the phosphines occupy axial sites in both compounds [27,33]
(Scheme 1).
2.89%. IR (m
CO, CH2Cl2): 1938 vs,br, 1917 sh cmÀ1; 1H NMR (CDCl3):
d 7.65 (m, 4H), 7.51 (m, 4H), 7.44 (m, 4H), 7.34 (m, 6H), 7.20 (m,
4H), À4.71 (t, J = 20.4 Hz, 1H); 31P-{1H} NMR (CDCl3): d À7.9 (s);
MS (FAB): m/z 820 (M+).
2.4. Reaction of [Mn2(CO)10] with PPhTh2
A
toluene solution (20 mL) of [Mn2(CO)10
]
(150 mg,
An additional product was isolated from the reaction of the
bis(acetonitrile) starting material, and it was shown to be fac-
[ClRe(CO)3(PPhTh2)2] (3) (21%) as confirmed by an X-ray crystallo-
graphic study. An ORTEP diagram of the molecular structure of 3 is
depicted in Fig. 1. and selected bond distances and angles are
listed in the caption. The basic structure of 3 is very similar to that
0.385 mmol) and PPhTh2 (106 mg, 0.386 mmol) was heated to re-
flux for 4 h. The solvent was removed under reduced pressure
and the residue chromatographed by TLC on silica gel. Elution with
hexane/CH2Cl2 (4:1, v/v) developed five bands. The first band gave
unreacted [Mn2(CO)10] (trace). The second, fourth and fifth bands
afforded [Mn2(CO)9(PhPTh2)] (7) (34 mg, 14%) as yellow crystals,
of the recently reported fac-[ClRe(CO)3(j
2-dppn)] (dppn = 1,8-
[Mn2(CO)6(
crystals and [Mn2(CO)5(PPhTh2}(
l
-PPhTh)(
l
-
g1
,
g
5-C4H3S)] (8) (98 mg, 46%) as orange
-PPhTh)(
5-C4H3S)] (9)
bis(diphenylphosphino)naphthalene) [34]. The molecule consists
of a single rhenium atom with three carbonyl groups arranged in
a facial arrangement, two PPhTh2 ligands and a chloride ligand.
The overall coordination geometry is a distorted octahedron which
is evident from the expansion of P–Re–P angle to 103.06(2)°, pre-
sumably a result of adverse steric interactions. The trans angles
about rhenium range from 168.6(3)° to 176.6(4)° which are com-
l
l- ,g
g1
(92 mg, 30%) as orange crystals after recrystallization from hex-
ane/CH2Cl2 at 4 °C. The third band gave a minor unidentified prod-
uct. Spectral data for 7: Anal. Calc. for C23H11Mn2O9PS2: C, 43.41; H,
1.74. Found: C, 43.75; H, 1.80%; IR (
m
(CO), CH2Cl2): 2091 m, 2064
w, 2012 s, 1993 vs, 1972 m, 1958 m, 1938 cmÀ1
;
1H NMR (CDCl3):
d 7.56 (m, 2H), 7.20 (m, 2H), 7.01 (m, 7H); 31P-{1H} NMR (CDCl3): d
58.6 (s); MS (FAB): m/z 636 (M+). Spectral data for 8: Anal. Calc. for
C20H11Mn2O6PS2: C, 43.49; H, 2.01. Found: C, 43.81; H, 2.07%; IR
parable to the corresponding angles in fac-[Re(CO)3(j -
1(P),g1
PPh2C10H6)(PPh2H)] which range from 168.62(9)° to 172.48(9)°
[34]. The rhenium–phosphorus distances of 2.494(2) Å and
2.520(2) Å are similar to those in reported in the literature for re-
lated complexes [25,27,33,34]. The source of the chloride ligand
was not identified; we speculate that it comes from the chlorinated
solvent during chromatographic separation or recrystallization.
The rhenium–chlorine bond distance of 2.514(4) Å is within the ex-
pected range [34]. Spectroscopic data for 3 are consistent with the
solid-state structure. The 1H NMR spectrum displays only aromatic
protons, while the 31P-{1H} NMR spectrum consists of a singlet at d
À15.1. The FAB mass spectrum shows a parent molecular ion at m/z
854.
(m ;
(CO), CH2Cl2): 2068 s, 1991 s, 1975 vs, 1961 vs, 1909 s cmÀ1
1H NMR (CDCl3): d 7.83 (m, 2H), 7.63 (m, 2H), 7.48 (m, 3H), 7.34
(m, 7H), 7.08 (s, br, 2H), 6.21 (s, br, 1H), 6.14 (s, br, 1H), 5.81 (m,
2H), 5.76 (s, br, 1H), 5.73 (s, br, 1H); 31P-{1H} NMR (CDCl3): d
À33.8 (s, 1P), À43.2 (s, 1P); MS (FAB): m/z 552 (M+). Spectral data
for 9: Anal. Calc. for C33H22Mn2O5P2S4: C, 49.63; H, 2.78. Found: C,
49.96; H, 2.85%; IR (m(CO), CH2Cl2): 2018 w, 1956 vs, 1931 vs, 1911
s, 1900 s cmÀ1; 1H NMR (CDCl3): d 7.88 (m, 2H), 7.76 (m, 2H), 7.54
(m, 4H), 7.50–7.27 (m, 24H), 7.12 (m, 4H), 7.04 (m, 2H), 5.85 (s, br,
1H), 5.75 (s, br, 1H), 5.66 (m, 2H), 5.55 (m, 1H), 5.52 (m, 1H); 31P-
{1H} NMR (CDCl3): d 51.4 (s, 2P), À12.9 (s, 1P), À21.6 (s, 1P); MS
(FAB): m/z 798 (M+).
3.2. Thermal reaction of [Re2(CO)10] and PhPTh2: selective carbon–
phosphorus bond scission
2.5. Conversion of 8–9
A toluene solution (15 mL) of 8 (50 mg, 0.091 mmol) was
heated to reflux for 3 h. Workup afforded unreacted 8 (trace) and
9 (39 mg, 54%).
Since at ambient temperature only simple substitution products
were observed, we investigated the elevated temperature reaction
between [Re2(CO)10] and PPhTh2. In refluxing xylene, both 2 (13%)

5178
S. Ghosh et al. / Inorganica Chimica Acta 362 (2009) 5175–5182
Table 1
Crystallographic data for compounds 3, 4, 6, 8 and 9.
Compound
3
4
6
8
9
Empirical formula
Formula weight (Å)
Temperature (K)
Wavelength (Å)
Crystal system
Space group
C31H22ClO3.30P2ReS4
859.04
100(2)
1.54178
monoclinic
Pn
C31H20O7P2Re2S3
1034.99
100(2)
1.54178
monoclinic
P21/n
C31H23O3P2ReS4
819.87
100(2)
1.54178
monoclinic
C2/c
C20H11Mn2O6PS2
552.26
100(2)
1.54178
monoclinic
P21/n
C33H22Mn2O5P2S4
798.57
100(2)
1.54178
monoclinic
P21/c
Unit cell dimensions
a (Å)
b (Å)
c (Å)
a (°)
9.5825(3)
8.8810(3)
18.6992(5)
90
13.2604(2)
11.4601(2)
22.4574(4)
90
16.8770(5)
9.6013(3)
19.6843(6)
90
15.9950(4)
9.0185(2)
16.0234(4)
90
18.2626(5)
11.8253(3)
17.0579(5)
90
b (°)
90.5420(10)
90
1591.27(8)
2
104.2630(10)
90
3307.55(10)
4
103.4030(10)
90
3102.79(16)
4
113.2600(10)
90
2123.53(9)
4
117.307(2)
90
3273.31(16)
4
c (°)
Volume (Å3)
Z
Density (calculated)
1.793
2.078
1.755
1.727
1.62
(Mg mÀ3
)
Absorption coefficient
(mmÀ1
F(0 0 0)
11.925
17.173
11.416
12.554
9.94
)
841
1960
1608
1104
1616
Crystal size (mm)
h range for data collection
(°)
0.37 Â 0.29 Â 0.04
0.42 Â 0.22 Â 0.10
0.23 Â 0.15 Â 0.10
0.49 Â 0.30 Â 0.20
0.40 Â 0.30 Â 0.20
4.73–66.91
4.06–68.02
4.62–67.17
3.31–61.48
2.72–61.32
Index ranges
À11 6 h 6 10,
À0 6 k 6 10,
À22 6 l 6 21
13161
À15 6 h 6 15,
0 6 k 6 13,
À19 6 h 6 19,
0 6 k 6 11,
–18 6 h 6 16,
0 6 k 6 10,
–20 6 h 6 18,
0 6 k 6 13,
0 6 l 6 26
0 6 l 6 22
0 6 l 6 18
0 6 l 6 19
Reflections collected
27360
12995
17449
26627
Independent reflections
5170 [Rint = 0.0214]
5915 [Rint = 0.0252]
2692 [Rint = 0.0177]
3225 [Rint = 0.0272]
4968 [Rint = 0.0391]
(Rint
)
Refinement method
full-matrix least-squares
on F2
5170/301/366
full-matrix least-
squares on F2
5915/182/389
full-matrix least-
squares on F2
2692/30/237
full-matrix least-
squares on F2
3225/30/226
full-matrix least-
squares on F2
4968/282/382
Data/restraints/
parameters
Goodness-of-fit (GOF) on
1.003
1.039
1.11
1.203
1.019
F2
Final R indices [I > 2s(I)]
R1 = 0.0185,
R1 = 0.0307,
R1 = 0.0155,
R1 = 0.0405,
R1 = 0.0621,
wR2 = 0.0457
R1 = 0.0189,
wR2 = 0.0736
R1 = 0.0323,
wR2 = 0.0391
R1 = 0.0156,
wR2 = 0.1003
R1 = 0.0414,
wR2 = 0.1474
R1 = 0.0666,
R indices (all data)
wR2 = 0.0459
0.622 and À0.410
wR2 = 0.0745
1.351 and À0.989
wR2 = 0.0392
0.503 and À0.330
wR2 = 0.1008
2.184 and À0.888
wR2 = 0.1502
0.830 and À0.937
Largest diff. peak and hole
(e ÅÀ3
)
25 oC
PPhTh2
MeCN
MeCN
Re
Re
CO
Th2PhP
Re
Re
CO
(CO)4
(CO)4
(CO)4
(CO)4
1
25 oC
2 PPhTh2
Re
(CO)4
Re
NCMe
Th2PhP
Re
(CO)4
Re
PPhTh2
(CO)4
(CO)4
2
+
CO
Re
OC
OC
PPhTh2
PPhTh2
Cl
3
Scheme 1.
and three new compounds were formed, viz. [Re2(CO)7(PPhTh2)
-PPhTh)( -H)] (4) (30%), [Re2(CO)7(PPhTh2)( -PPhTh)(
1(S)-C4H3S)] (5) (19%) and mer-[HRe(CO)3(PPhTh2)2] (6) (17%)
(Scheme 2).
All three new compounds have been characterized by elemental
analysis and spectroscopic data, as well as single crystal X-ray dif-
fraction studies for 4 and 6. An ORTEP diagram of the molecular
structure of 4 is depicted in Fig. 2. The disordered crystal contains
two enantiomers, each containing a dirhenium core with seven ter-
minal carbonyl groups, a bridging phenyl(2-thienyl)phosphido
group, an intact PPhTh2 ligand and a bridging hydride. The hydride
ligand was located and refined in the structural analysis [Re(1)–
H(1H) 1.90(7) Å and Re(2)–H(1H) 1.92(7) Å]. The phenyl(2-thie-
nyl)phosphido ligand bridges the rhenium–rhenium vector some-
what asymmetrically [Re(1)–P(1) 2.3923(13) Å and Re(2)–P(1)
2.4336(13) Å] and the PPhTh2 ligand occupies an equatorial site
(
j
l
l
l
l- ,
g1

S. Ghosh et al. / Inorganica Chimica Acta 362 (2009) 5175–5182
5179
Fig. 1. Molecular structure of fac-[ClRe(CO)3(PPhTh2)2] (3) showing 50% probability
thermal ellipsoids. Ring hydrogens are omitted for clarity. Selected bond lengths (Å)
and angles (°): Re(1)–P(1) 2.494(2), Re(1)–P(2) 2.520(2), Re(1)–Cl(1) 2.514(4),
Re(1)–C(1) 1.917(9), Re(1)–C(2) 1.961(7), Re(1)–C(3) 1.961(10), C(1)–Re(1)–C(2)
89.6(4), C(1)–Re(1)–C(3) 91.2(5), C(2)–Re(1)–C(3) 86.64(12), C(1)–Re(1)–P(1)
82.8(4), C(1)–Re(1)–P(2) 97.5(4), C(2)–Re(1)–P(1) 168.8(2), C(3)–Re(1)–P(1)
85.3(3), C(2)–Re(1)–P(2) 86.0(3), C(3)–Re(1)–P(2) 168.6(3), C(1)–Re(1)–Cl(1)
176.6(4), C(2)–Re(1)–Cl(1) 92.7(2), C(3)–Re(1)–Cl(1) 91.4(2), P(1)–Re(1)–Cl(1)
95.22(8), Cl(1)–Re(1)–P(2) 80.22(9), P(1)–Re(1)–P(2) 103.06(2), O(1)–C(1)–Re(1)
174.9(12), O(2)–C(2)–Re(1) 175.1(7), O(3)–C(3)–Re(1) 174.3(8).
Fig. 2. Molecular structure of [Re2(CO)7(PPhTh2)(
l
-PPhTh)(
l
-H)] (4) showing 50%
probability thermal ellipsoids. Ring hydrogens are omitted for clarity. Selected bond
lengths (Å) and angles (°): Re(1)–Re(2) 3.1497(3), Re(1)–P(1) 2.3923(13), Re(1)–P(2)
2.4162(12), Re(2)–P(1) 2.4336(13), Re(1)–H(1H) 1.90(7), Re(2)–H(1H) 1.92(7),
C(2)–Re(1)–C(3) 88.8(2), C(2)–Re(1)–C(1) 87.6(2), C(3)–Re(1)–C(1) 176.4(2), C(2)–
Re(1)–P(1) 100.08(15), C(3)–Re(1)–P(1) 91.09(15), C(1)–re(1)–P(1) 90.17(16), C(2)–
Re(1)–P(2) 96.31(15), C(3)–Re(1)–P(2) 86.56(15), C(1)–Re(1)–P(2) 93.19(15), P(1)–
Re(1)–P(2) 163.39(4), P(1)–Re(1)–Re(2) 49.83(3), P(1)–Re(2)–Re(1) 48.69(3), P(1)–
Re(1)–H(1H) 84(2), P(1)–Re(2)–H(1H) 83(2), P(2)–Re(1)–H(1H) 80(2), C(7)–Re(2)–
H(1H) 83(2), C(2)–Re(1)–H(1H) 174(2), C(5)–Re(2)–H(1H) 176(2), Re(2)–Re(1)–
H(1H) 35(2), Re(1)–Re(2)–H(1H) 34(2), C(7)–Re(2)–P(1) 165.63(19), C(6)–Re(2)–
P(1) 89.35(17), C(5)–Re(2)–P(1) 100.5(2), C(5)–Re(2)–C(7) 93.8(3), C(5)–Re(2)–C(6)
89.1(3), C(5)–Re(2)–C(4) 91.5(3), C(6)–Re(2)–C(4) 178.1(2), Re(1)–P(1)–Re(2)
81.48(4), C(14)–P(1)–C(8) 104.6(5).
Ph
Th
P
140 oC
PPhTh2
[Re2(CO)10
]
(OC)3Re
Th2PhP
Re(CO)4
2
+
H
4
CO
Th2PhP
S
OC
Th2PhP
+
(OC)
(CO)
Re
PPhTh2
CO
3Re
Re
H
4
P
Th
Ph
6
5
Scheme 2.
Chart 3.
and lies trans to the phosphido-bridge [P(1)–Re(2)–P(2)
163.39(4)°]. The Re–Re bond length of 3.1497(3) Å is similar to that
which are assigned to the phenyl and thienyl ring protons. In addi-
tion, the multiplet at d 6.38 (integrating to 1H) is indicative of an
orthometallated thienyl or phenyl ring. The 31P-{1H} NMR spec-
trum again indicates the presence of two isomers in solution in
an approximate 20:1 ratio. The major isomer shows doublets at d
À21.0 and À55.9 (JPP = 98.0 Hz), while the minor exhibits doublets
at d À19.1 (J = 116.4 Hz) and À53.7 (JPP = 116.4 Hz); these isomers
are probably isomers (diastereomers) of the same kind observed
for 4, but may also be diastereomers formed by the combination
of the stereogenic centers at the sulfur and the bridging phosphido
moiety (or combinations of these types of isomers). The FAB mass
spectrum shows a molecular ion at m/z 1118 and fragmentation
ions due to sequential loss of seven carbonyl groups. Elemental
analysis (cf. Section 2.3) was also consistent with the empirical
formula.
An ORTEP diagram of the molecular structure of 6 is shown in
Fig. 3. and selected bond distances and angles are listed in the cap-
tion. The molecule has two crystallographic planes of symmetry
and contains a single rhenium atom ligated by three carbonyls,
two phosphines and a hydride. The latter was located and refined
in the structural analysis [Re(1)–H(1H) 1.73(6) Å]. The PPhTh2 li-
gands lie trans [P(1)–Re(1)–P(1)#1 166.47(3)°] presumably to
minimize steric hindrance. While in 3 the carbonyls are arranged
in a facial fashion in 6 they adopt a meridional arrangement. The
found in [Re2(CO)7(PTh3)(l-PTh2)(l-H)] (I) [3.1555(2) Å] (Chart 2)
and the IR spectrum also closely resembles that of I [33]. In the so-
lid-state structure the thienyl and phenyl groups are clearly distin-
guished, but occupy chemically inequivalent sites. The 31P-{1H}
NMR spectrum clearly indicates the existence of two isomeric
forms in solution in an approximate 10:1 ratio. The major isomer
(probably that seen in the solid-state (4a, Chart 3), with the phos-
phine in relative trans position to the thienyl substituent of the
bridging phosphido moiety), consists of two doublets at d 24.1
and À18.4 (JPP = 70.4 Hz), while there is also a second set of dou-
blets at d À8.4 and À17.9 (JPP = 76.4 Hz) attributed to the minor
isomer (Chart 3). Both sets of signals are sharp and we have no evi-
dence for the interconversion of the two. Apparently, this isomer
has the phosphine in the cis position relative to the bridging phos-
phido moiety. Steric crowding of the P–P groupings gives energies
of 861 vs. 843 kJ/mol for the trans isomer. The crystal of 4a con-
tains two enantiomers in a 50/50 ratio (Chart 3).
All attempts to obtain single crystals of 5 suitable for X-ray dif-
fraction analysis were unsuccessful and characterization has there-
fore been made on the basis of analytical and spectroscopic data.
The IR spectrum is very similar to that of [Re2(CO)7(PTh3)(l-
PTh2)(l- ,j
g1 1(S)-C4H3S)] (J) (Chart 2), indicating that the two are
isostructural. The 1H NMR spectrum shows seven multiplets in
the aromatic region with the relative intensity of 3:5:3:5:4:1:1

5180
S. Ghosh et al. / Inorganica Chimica Acta 362 (2009) 5175–5182
plays only a singlet at d 58.6 and the FAB mass spectrum exhibits
a parent molecular ion at m/z 636 consistent with the proposed
structure.
An ORTEP diagram of the molecular structure of 8 is shown in
Fig. 4. and selected bond distances and angles are listed in the cap-
tion. The molecule consists of a dinuclear framework of two man-
ganese atoms coordinated by six carbonyl groups, a phenylthienyl
phosphido bridge and a thienyl bridge. The structure is very similar
to the PPh2Th and PTh3 analogs [Mn2(CO)6(
C4H3S)] (D) (Chart 1) and [Mn2(CO)6( -PTh2)(
(Chart 2). The phosphido ligand bridges the dimanganese center
[Mn...Mn 3.510(1) Å] quite asymmetrically [Mn(1)–P(1)
2.3711(11) Å and Mn(2)–P(1) 2.2848(11) Å]. The bridging thienyl
l
-PPh2)(
l- , -
g1 g5
l
l- ,g
g1 5-C4H3S)] (O)
ligand is bound to one manganese atom by a simple
[Mn(1)–C(10) 2.079(4) Å], but it binds to the second in an
r
g
-bond
5-fash-
ion with manganese–carbon bond distances ranging between
2.129(4) and 2.195(4) Å. This is very similar to the situation found
in D and O and we therefore conclude that it acts as an overall 7-
electron donor ligand. As a result, Mn(1) has an octahedral coordi-
nation sphere, while Mn(2) possesses a half-sandwich geometry.
Both 1H NMR and 31P-{1H} NMR spectra suggest that it exists in
two isomeric (diastereomeric) forms in solution. For example, the
latter spectrum shows two equal intensity singlets at d À33.8
and À43.2. As discussed above, it is likely that the diastereomers
are formed by the combination of the stereogenic centers at the
sulfur and the bridging phosphido moiety (or combinations of
Fig. 3. Molecular structure of mer-[HRe(CO)3(PPhTh2)2] (6) showing 50% probabil-
ity thermal ellipsoids. Ring hydrogens are omitted for clarity. Selected bond lengths
(Å) and angles (°): Re(1)–P(1) 2.3849(5), Re(1)–P(1)#1 2.3849(5), Re(1)–H(1H)
1.73(6), Re(1)–C(1) 1.957(3), Re(1)–C(2) 1.986(2), Re(1)–C(2)#1 1.986(2), C(1)–
Re(1)–C(2) 93.41(6), C(1)–Re(1)–C(2)#1 93.41(6), C(2)–Re(1)–C(2)#1 173.18(12),
C(1)–Re(1)–P(1) 96.767(13), C(1)–Re(1)–P(1)#1 96.766(12), C(2)–Re(1)–P(1)
91.11(6), C(2)#1–Re(1)–P(1) 88.09(6), C(2)–Re(1)–P(1)#1 88.09(6), C(2)#1–Re(1)–
P(1)#1 91.10(6), C(1)–Re(1)–H(1H) 180.00(2), C(2)–Re(1)–H(1H) 86.59(6), C(2)#1–
Re(1)–H(1H) 86.59(6), P(1)–Re(1)–H(1H) 83.233(13), P(1)#1–Re(1)–H(1H)
83.23(2), P(1)–Re(1)–P(1)#1 166.47(3), O(1)–C(1)–Re(1) 180.000(1), O(2)–C(2)–
Re(1) 177.24(19).
these types of isomers). The
p-complexation of a thienyl ring is
also indicated by the upfield resonances in the1H NMR spectrum
at d 6.21, 6.14, 5.81, 5.76 and 5.73 in a 1:1:2:1:1 ratio. The FAB
mass spectrum exhibits a parent molecular ion at m/z 552 plus
other ions due to stepwise loss of six carbonyl ligands, which is
in accord with the solid-state structue.
structure is very similar to that of mer-[HRe(CO)3(PPh3)2] [35] and
mer-[HRe(CO)3(PTh3)2] [27]. Spectroscopic data suggests that the
solid-state structure persists in solution. The 1H NMR spectrum
shows a triplet at d À4.71 (JPH = 20.4 Hz) due to the hydride, while
the 31P{1H} NMR spectrum contains only a singlet at d À7.9 due to
two equivalent phosphorus atoms.
An ORTEP diagram of the molecular structure of 9 is shown in
Fig. 5. and selected bond distances and angles are listed in the cap-
3.3. Reaction of [Mn2(CO)10] with PPhTh2: carbon–phosphorus bonds
cleavage
Since the reactivity of [Mn2(CO)10] with PPh2Th [25] closely
parallels that established previously for PTh3 [27], we also con-
ducted for comparison the reaction of [Mn2(CO)10] with PPhTh2.
In refluxing toluene three new complexes were formed, namely
[Mn2(CO)9(PPhTh2)] (7) (14%), [Mn2(CO)6(
C4H3S)] (8) (46%) and [Mn2(CO)5(PPhTh2)(
l
l
-PPhTh)(
l
-
-
g1
,
,
g5
-
-
-PPhTh)(
l
g1
g5
C4H3S)] (9) (30%) (Scheme 3). In a separate experiment we also
showed that 8 is converted into 9 when treated with PPhTh2 under
the same conditions. These results are similar to those observed for
PTh3 [27]. The structure of 7 is easily assigned on the basis of spec-
troscopic data - the IR spectrum being very similar to other substi-
tuted [Mn(CO)9L] compounds (L = PTh3, PPhTh2, diphenyl(1-
naphthyl)phosphine) [25,27,34]. The 31P-{1H} NMR spectrum dis-
110 oC
(CO)4
[Mn2(CO)10
]
(OC)5Mn
Mn
PPhTh2
PPhTh2
7
Fig. 4. Molecular structure of [Mn2(CO)6(l-PPhTh)(l- ,g
g1 5-C4H3S)] (8) showing
S
50% probability thermal ellipsoids. Ring hydrogens are omitted for clarity. Selected
bond lengths (Å) and angles (°): Mn(1)–P(1) 2.3711(11), Mn(2)–P(1) 2.2848(11),
Mn(2)–S(1) 2.3084(10), Mn(2)–C(7) 2.129(4), Mn(2)–C(8) 2.156(4), Mn(2)–C(9)
2.177(4), Mn(2)–C(10) 2.195(4), Mn(1)–C(10) 2.079(4), C(3)–Mn(1)–C(2) 95.35(17),
C(1)–Mn(1)–C(4) 176.33(16), C(3)–Mn(1)–C(10) 171.62(16), C(2)–Mn(1)–C(10)
92.85(16), C(3)–Mn(1)–P(1) 96.13(13), C(2)–Mn(1)–P(1) 168.29(12), C(10)–
Mn(1)–P(1) 75.76(10), C(1)–Mn(1)–P(1) 86.82(12), C(1)–Mn(1)–C(10) 92.89(15),
C(5)–Mn(2)–P(1) 93.65(13), C(6)–Mn(2)–P(1) 99.04(12), C(5)–Mn(2)–C(6)
88.73(18), C(10)–Mn(2)–P(1) 75.44(10), P(1)–Mn(2)–S(1) 92.31(4), Mn(2)–P(1)–
Mn(1) 97.86(4), Mn(1)–C(10)–Mn(2) 110.40(16), C(20)–P(1)–C(11) 101.1(4).
S
Th2PhP
(OC)
Mn(CO)2
4 Mn
+
Mn(CO)2
Mn
P
(CO)3
P
Th Ph
Ph
Th
110 oC
PPhTh2
8
9
Scheme 3.

S. Ghosh et al. / Inorganica Chimica Acta 362 (2009) 5175–5182
5181
Acknowledgements
N.B. thanks Sher-e-Bangla Agricultural University for leave to
work at Lund University. This research has been sponsored by
the Swedish Research Council (VR), the Royal Swedish Academy
of Sciences, the Swedish International Development Agency (SIDA)
and Ministry of Science and Information & Communication Tech-
nology, Government of the People’s Republic of Bangladesh.
References
[1] H. Topsøe, B.A. Clausen, F.E. Massoth, Hydrotreating Catalysis, Springer, Berlin,
1996.
[2] J.G. Speight (Ed.), Petroleum Chemistry and Refining, Taylor and Francis,
Washington, DC, 1998.
[3] R.J. Angelici, in: R.B. King (Ed.), Encyclopedia of Inorganic Chemistry, vol. 3,
Wiley, New York, 1994, pp. 1433–1443.
[4] (a) D.D. Whitehurst, T. Isoda, I. Mochida, Adv. Catal. 42 (1998) 345;
(b) M.J. Ledoux, O. Michaux, G. Agostini, P. Panissod, J. Catal. 102 (1986) 275.
[5] (a) B.C. Gates, J.R. Katzer, G.C.A. Schuit, Chemistry of Catalytic Processes,
McGraw-Hill, New York, 1979. pp. 390–447;
(b) G.D. Galpern, in: S. Gronowitz (Ed.), The Chemistry of Heterocyclic
Compounds, vol. 44, Part 1, Wiley, New York, 1985, pp. 325–351.
[6] (a) R.A. Sanchez-Delgado, J. Mol. Catal. 86 (1994) 287;
(b) R.J. Angelici, Polyhedron 16 (1997) 3073;
(c) C. Bianchini, A. Meli, J. Chem. Soc., Dalton Trans. (1996) 801.
[7] (a) R.D. Adams, O.-S. Kwon, J.L. Perrin, J. Organomet. Chem. 596 (2000) 102;
(b) R.D. Adams, X. Qu, Organometallics 14 (1995) 2238.
[8] (a) T.A. Pecoraro, R.R. Chianelli, J. Catal. 67 (1981) 430;
(b) R.R. Chianelli, Catal. Rev. 26 (1984) 361;
Fig. 5. Molecular structure of [Mn2(CO)5(PPhTh2)(l-PPhTh)(l- ,g
g1 5-C4H3S)] (9)
showing 50% probability thermal ellipsoids. Ring hydrogens are omitted for clarity.
Selected bond lengths (Å) and angles (°): Mn(1)–P(1) 2.2880(15), Mn(1)–P(2)
2.3471(15), Mn(2)–P(2) 2.241(2), Mn(2)–S(4) 2.295(4), Mn(1)–C(30) 2.080(10),
Mn(2)–C(30) 2.198(12), Mn(2)–C(31) 2.186(11), Mn(2)–C(32) 2.161(11), Mn(2)–
C(33) 2.119(11), C(1)–Mn(1)–C(3) 174.2(2), C(2)–Mn(1)–C(30) 169.5(4), C(2)–
Mn(1)–P(1) 97.98(18), C(30)–Mn(1)–P(1) 90.7(4), C(30)–Mn(1)–P(2) 75.9(4),
P(1)–Mn(1)–P(2) 165.69(6), C(1)–Mn(1)–P(2) 92.02(16), C(1)–Mn(1)–P(1)
92.03(16), C(1)–Mn(1)–C(30) 86.0(4), C(4)–Mn(2)–C(5) 89.3(7), C(4)–Mn(2)–P(2)
91.6(4), C(5)–Mn(2)–P(2) 97.3(4), P(2)–Mn(2)–S(4) 92.57(10), Mn(2)–P(2)–Mn(1)
98.28(7), Mn(1)–C(30)–Mn(2) 108.4(6), C(24)–P(2)–C(20) 95.8(9).
(c) C. Bianchini, A. Meli, Acc. Chem. Res. 31 (1998) 109;
(d) T.B. Rauchfuss, Prog. Inorg. Chem. 39 (1991) 259;
(e) D.A. Vicic, W.D. Jones, J. Am. Chem. Soc. 121 (1999) 7606.
[9] (a) R.J. Angelici, Acc. Chem. Res. 21 (1988) 387;
tion. The structure is related to that of 8 in with a PPhTh2 ligand
replacing an equatorial CO group on Mn(1) that lies trans to the
phosphido bridge. This structure is also very similar to that of
(b) N.N. Sauer, R.J. Angelici, J. Catal. 116 (1989) 11;
(c) J.J. Garcia, B.E. Mann, H. Adams, N.A. Bailey, P.M. Maitlis, J. Am. Chem. Soc.
117 (1995) 2179;
[Mn2(CO)5(PTh3)(l-PTh2)(l- ,g
g1 5-C4H3S)] (9) (P) (Chart 2) This
(d) R.J. Angelici, Organometallics 20 (2001) 1259. and references therein.
[10] (a) R.J. Angelici, Coord. Chem. Rev. 105 (1990) 61;
(b) R.J. Angelici, Coord. Chem. Rev. 206–207 (2000) 63.
[11] M. Brorson, J.D. King, K. Kiriakidou, F. Prestopino, E. Nordlander, in: P.
Braunstein, L.A. Oro, P.R. Raithby (Eds.), Metal Clusters in Chemistry, vol. 2,
Wiley-VCH, Weinheim, 1999, pp. 741–781. Chapter 2.6.
[12] (a) R.J. Angelici, Transition Metal Sulphides, NATO ASI Ser 3, vol. 60, 1998, p.
89;
complex is disordered in the crystal so that the two diastereomers
overlap in a 50/50 ratio. In addition the crystal is centric so that
there is an exact 50/50 ratio of the enantiomeric forms of each dia-
stereomer. The 31P-{1H} NMR spectrum displays three resonances
at d 51.4, À12.9 and À21.6 in a 2:1:1 ratio. The FAB mass spectrum
exhibits the parent molecular ion at m/z 798 together with ions
due to successive loss of five carbonyl ligands which is consistent
with the solid-state structue.
(b) C. Bianchini, A. Meli, Transition Metal Sulphides, NATO ASI Ser. 3, vol. 60,
1998, p. 129;
(c) R.J. Angelici, Bull. Soc. Chim. Belg. 104 (1995) 265.
[13] (a) P.A. Vecchi, A. Ellern, R.J. Anjelici, Organometallics 24 (2005) 2168;
(b) P.A. Vecchi, A. Ellern, R.J. Anjelici, J. Am. Chem. Soc. 125 (2003) 2064.
[14] (a) H. Li, K. Yu, E.J. Watson, K.L. Virkaitis, J.S. D’Acchioli, G.B. Carpenter, D.A.
Sweigart, Organometallics 21 (2002) 1262;
(b) A.J. Hernández-Maldonado, R.T. Yang, J. Am. Chem. Soc. 126 (2004) 992.
[15] (a) M.A. Reynolds, I.A. Guzei, R.J. Angelici, J. Am. Chem. Soc. 124 (2002) 1689;
(b) M.A. Reynolds, I.A. Guzei, R.J. Angelici, Organometallics 20 (2001) 1071.
[16] (a) D.G. Churchill, B.M. Bridgewater, G. Parkin, J. Am. Chem. Soc. 122 (2000)
178;
4. Conclusion
In summary, we have demonstrated the reactivity of PPhTh2 to-
wards [Re2(CO)10Àx(NCMe)x] (x = 0, 1, 2) and [Mn2(CO)10]. Under
mild conditions, reactions with the lightly stabilized rhenium com-
plexes give simple substitution products, but carbon–phosphorus
bond cleavage is observed under more forcing conditions. Reaction
of [Mn2(CO)10] with PPhTh2 affords three dimanganese complexes
of which compounds 8 and 9 have been obtained as a result of car-
bon–phosphorus bond cleavage and each contains a bridging thie-
(b) M.S. Palmer, S. Harris, Organometallics 19 (2000) 2114;
(c) J. Torres-Nieto, A. Arévalo, P. García-Gutiérrez, A. Acosta-Ramírez, J.J.
García, Organometallics 23 (2004) 4534.
[17] (a) K. Bieger, F. Estevan, P. Lahuerta, J. Lloret, J. Pérez-Prieto, M. Sanaú, N.
Siguero, S.-E. Stiriba, Organometallics 22 (2003) 1799;
(b) J. Lloret, F. Estevan, P. Lahuerta, P. Hirva, J. Pérez-Prieto, M. Sanaú,
Organometallics 25 (2006) 3156.
[18] A.J. Deeming, S.N. Jayasuriya, A.J. Arce, Y.D. Sanctis, Organometallics 15 (1996)
786.
[19] J.D. King, M. Monari, E. Nordlander, J. Organomet. Chem. 573 (1999) 272.
[20] N.K. Kiriakidou Kazemifar, M.J. Stchedroff, M.A. Mottalib, S. Selva, M. Monari, E.
Nordlander, Eur. J. Inorg. Chem. (2006) 2058.
[21] S.P. Tunik, I.G. Koshevoy, A.J. Poë, D.H. Farrar, E. Nordlander, M. Haukka, P.A.
Pakkanen, J. Chem. Soc., Dalton Trans. (2003) 2457.
nyl ligand bonded to one manganese atom in a
g
5-fashion. This
observation is similar to that reported for PPh2Th [25] and PTh3
[27]. We note that in all instances it is the phosphorus–thienyl
bond that is cleaved.
[22] N.K. Kiriakidou Kazemifar, M.J. Stchedroff, M.H. Johannson, M.A. Mottalib, M.
Monari, E. Nordlander, Unpublished results.
[23] M.A. Mottalib, S.E. Kabir, D.A. Tocher, A.J. Deeming, E. Nordlander, J.
Organomet. Chem. 692 (2007) 5007.
Supplementary material
CCDC 667828, 694818, 667827, 634409 and 634410 contain the
supplementary crystallographic data for 3, 4, 6, 8 and 9, respec-
tively. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
[24] U. Bodensieck, H. Varenkamp, G. Rheinwald, H. Stoeckli-Evans, J. Organomet.
Chem. 488 (1995) 85.
[25] A.J. Deeming, M.K. Shinhmar, A.J. Arce, Y.D. Sanctis, J. Chem. Soc., Dalton Trans.
(1999) 1153.
[26] M.N. Uddin, N. Begum, M.R. Hassan, G. Hogarth, S.E. Kabir, M.A. Miah, E.
Nordlander, D.A. Tocher, J. Chem. Soc., Dalton Trans. (2008) 6219.

5182
S. Ghosh et al. / Inorganica Chimica Acta 362 (2009) 5175–5182
[27] M.N. Uddin, M.A. Mottalib, N. Begum, S. Ghosh, A.K. Raha, D.T. Haworth, S.V.
Lindeman, T.A. Siddiquee, D.W. Bennett, G. Hogarth, E. Nordlander, S.E. Kabir,
Organometallics 28 (2009) 1514.
[28] (a) U. Koelle, J. Organomet. Chem. 155 (1978) 53;
(b) G.W. Harris, J.C.A. Boeyens, N.J. Coville, J. Chem. Soc., Dalton Trans. (1985)
2277;
(c) D.R. Grad, T.L. Brown, J. Am. Chem. Soc. 104 (1982) 6340.
[29] SAINT Software for CCD Diffractometer, V.7.23A, Bruker AXS, 2005.
[30] G.M. Sheldrick, SADBS-2004/1, Program for empirical absorption correction of
area-detector data, Institüt für Anorganische Chemie der Universität,
Göttingen, Germany, 2005.
[31] Program XS from SHELXTL package, V. 6.12, Bruker AXS, 2001.
[32] Program XL from SHELXTL package, V. 6.10, Bruker AXS, 2001.
[33] M. Khatun, S. Ghosh, D.T. Haworth, S.V. Lindeman, T.A. Siddiquee, D.W.
Bennett, G. Hogarth, E. Nordlander, S.E. Kabir, J. Organomet. Chem. 694 (2009)
2941.
[34] S.E. Kabir, F. Ahmed, S. Ghosh, M.R. Hassan, M.S. Islam, A. Sharmin, D.A. Tocher,
D.T. Haworth, S.V. Lindeman, T.A. Siddiquee, D.W. Bennet, K.I. Hardcastle, J.
Organomet. Chem. 693 (2008) 2657.
[35] U. Flörke, H.J. Haupt, Z. Kristallogr. 201 (1992) 317.