A synthetic and X-ray crystallographic study of the indenyl-phosphine complexes 1,3-(Ph2P=X)2(C9H6), (X=O, S) and (η5-C9H5(Ph2P=S)2)[Mn (CO)3]: V

Article abstract of DOI:10.1016/S0022-328X(98)00648-2

The syntheses and X-ray crystal structures of the oxidized indenyl-diphosphines, 1,3-(Ph₂P=X)₂C₉H₆, where X is O, S, are reported. The sulfur complex is readily deprotonated to form the corresponding 1,3-disubst

Full text of DOI:10.1016/S0022-328X(98)00648-2

Journal of Organometallic Chemistry 564 (1998) 101–108
A synthetic and X-ray crystallographic study of the indenyl-phosphine
complexes 1,3-(Ph2P.X)2(C9H6), (X=O, S) and
(p5-C9H5(Ph2P.S)2)[Mn(CO)3]: versatile ligands for the preparation of
heteropolymetallic complexes
Mark Stradiotto, Christopher M. Kozak, Michael J. McGlinchey *
Department of Chemistry, McMaster Uni6ersity, Hamilton, Ontario L8S 4M1, Canada
Received 12 February 1998; received in revised form 21 April 1998
Abstract
The syntheses and X-ray crystal structures of the oxidized indenyl-diphosphines, 1,3-(Ph2P.X)2C9H6, where X is O, S, are
reported. The sulfur complex is readily deprotonated to form the corresponding 1,3-disubstituted indenide anion, which yields a
crystallographically-characterized p5-Mn(CO)3 complex upon treatment with bromopentacarbonylmanganese. The relevance of
these molecules to mixed-metal catalytic systems is discussed. © 1998 Elsevier Science S.A. All rights reserved.
Keywords: Indenyl-phosphine complexes; Versatile ligands; Crystal structures
1. Introduction
diphenylphosphinocyclopentadienyl (dppc) ligand, have
proven extremely effective in the construction of con-
strained polymetallic systems in which transition metals
are held in close proximity [4,5]. In the case of hetero-
bimetallic systems, the dppc ligand typically coordi-
nates to an ‘early’ transition metal in an p5-fashion via
the cyclopentadienyl fragment and to a ‘late’ transition
metal through the phosphine moiety. The versatility of
the dppc ligand and its derivatives is exemplified by the
numerous reports on the synthesis and catalytic proper-
ties of complexes derived from the commercially avail-
able 1,1%-bis(diphenylphosphino)ferrocene (dppf) [6]
fragment, as well as many other homopolymetallic [4]
and heteropolymetallic [5] systems. Moreover, the
chemistry of such dppc-based systems has been further
expanded via oxidation, which transforms the phospho-
rus center into an oxygen or sulfur donor ([1], [2]a, [5]c,
[7]), while the incorporation of two phosphine units
onto a single cyclopentadiene ring has allowed for the
formation of chelates [1].
The preparation of heteropolyfunctional ligands has
attracted considerable interest recently, as a result of
their utility in the formation of homo- and bimetallic
complexes [1,2]. Such bi- and trimetallic systems in
which the metal centers possess markedly different elec-
tron counts are thought to be attractive synthetic
targets, in that the metal centers have the potential to
interact in a simultaneous and cooperative fashion in
the activation of organic substrates [3]. The successful
preparation of suitable polymetallic complexes necessi-
tates that the metal centers be rigidly linked, such that
the structural integrity of the catalyst is maintained
throughout the catalytic process.
Polyfunctional ligands which incorporate both cy-
clopentadienyl and phosphine moieties, such as the
* Corresponding author. Tel.: +1 905 5259140, ext. 24504; fax:
+1 905 5222509; e-mail: mcglinc@mcmaster.ca
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00648-2

102
M. Stradiotto et al. / Journal of Organometallic Chemistry 564 (1998) 101–108
Scheme 1. The preparation of compounds 1, 2 and 3.
Although cyclopentadienyl-based ligands have re-
trimethylsilylindene produces approximately equimolar
amounts of the 1,1 and 1,3 isomers of bis(trimethylsi-
lyl)indene, which interconvert via silatropic shifts
(Scheme 2) [13]. In addition to the increased steric
demand of the diphenylphosphino fragment relative to
the trimethylsilyl unit at the C-1 position of the substi-
tuted indene, such an observation can be rationalized in
terms of the propensity of 1-(diphenylphosphino)indene
to rearrange to the thermodynamically-favored 3-
(diphenylphosphino) isomer, even at ambient tempera-
ture [8]. While such a rearrangement involves the
overall transfer of a proton from C-1 to C-3, it is
unlikely to proceed at low temperatures via sequential
[1,5]-sigmatropic shifts, given the large activation en-
ergy associated with these processes. However, it is
possible to envisage an acid- or base-catalyzed proton
transfer mechanism, mediated by zwitterionic or Wittig-
type intermediates (Scheme 3) [14], which would be
available to the phosphine but not the silane [15]. It has
also been demonstrated by Broussier and co-workers
that an sp3-substituted product is formed upon quench-
ing of the 1, 2, 3-trimethylcyclopentadienyl anion with
chlorodiphenyphosphine at −10°C, whereas sp2-bound
phosphines are formed when the analogous reaction is
carried out under ambient conditions [1].
ceived much attention, there exists a paucity of reports
on the chemistry of systems which incorporate the
corresponding indenyl framework [8,9]. Given the
heightened catalytic activity exhibited by indenyl-based
ansa-bridged metallocenes in the stereospecific poly-
merization of alkenes [10], and our continued interest in
the synthesis and study of main-group and transition
metal indenyl complexes [11], we chose to probe the
utility of the 1,3-bis(diphenylphosphino)indene (bdppi)
ligand, 1, with respect to the preparation of constrained
polymetallic systems. Herein we report the synthesis
and characterization of bdppi, its oxidation products,
and some preliminary results concerning the prepara-
tion of transition metal derivatives of these ligands.
2. Results and discussion
The diphosphine, 1, is readily preparable by treat-
ment of 1-(diphenylphosphino)-indene [8] with one mo-
lar equivalent of n-BuLi, followed by quenching with
chlorodiphenylphosphine. Such air-sensitive solutions
of 1 can either be used directly in the preparation of
organometallic complexes [12], or converted cleanly to
the corresponding dioxide, 2, or disulfide, 3, as depicted
in Scheme 1.
The molecular structures of 2 and 3 were initially
elucidated based upon NMR spectroscopic data, in-
cluding those obtained by use of 31P{1H} selective
decoupling and two-dimensional NMR experiments.
The observed deshielding of l31P on going from the
Interestingly, the preparation of 1, 2 or 3 gives rise
exclusively to the 1,3-disubstituted product, whereas the
addition of a second trimethylsilyl substituent to

M. Stradiotto et al. / Journal of Organometallic Chemistry 564 (1998) 101–108
103
Scheme 2. The interconversion of 1,1- and 1,3-bis(trimethylsilyl)indene, via silatropic shifts.
Scheme 3. Possible Wittig-type intermediates in the isomerization of 1-(diphenylphosphino)indene to 3-(diphenylphosphino)indene.
dioxide, 2 (32.0 and 22.1 ppm), to the disulfide, 3 (46.9
and 32.5 ppm), is the same as that observed for the
corresponding oxidized triphenylphosphine systems
[16], while the observation that l31P(sp3)\l31P(sp2) is
a trend which is evident in related systems [1,8]. Both
high and low resolution mass spectrometric data ob-
tained for 2 and 3 are in agreement with these NMR
spectroscopic data.
The solid-state structures of 2 and 3 were unambigu-
ously determined by use of single-crystal X-ray diffrac-
tion techniques, and are presented in Figs. 1 and 2;
important crystallographic parameters and selected geo-
metrical data are summarized in Tables 1–5, respec-
Treatment of 3 with one molar equivalent of n-BuLi,
followed by quenching with Mn(CO)5Br yields the
organometallic complex, 4, which has been unequivo-
cally characterized by use of NMR spectroscopy and
X-ray crystallography (Scheme 4). From the structure
presented in Fig. 3 it can be observed that, in the solid
state, 4 deviates only modestly from ideal Cs symmetry.
In addition, close inspection of the bond lengths in 4
reveals that the bonding of the metal center has
‘slipped’ [17] slightly from p5 to p3, while the uncom-
plexed C6 ring of the indenyl unit clearly contains a
diene moiety, which could be utilized in complexation
of an additional metal center [18].
tively. The crystal structures of
2 and 3 fully
corroborate the aforementioned spectroscopic data, and
possess features which are generally quite similar to
those previously reported for related complexes ([6]c,
[8]). Although gratified by the geometric confirmation
provided by these structural determinations, the steri-
cally-demanding nature of the diphenylphosphino frag-
ments in both 2 and 3 prompted us to question the
accessibility of the C5 ring. Towards this end, an at-
tempt was made to complex a transition metal onto the
indenyl five-membered ring.
3. Summary
The numerous coordination modes available to the
indenyl ligand make it a logical candidate in the at-
tempt to expand the organometallic chemistry of cy-
clopentadienyl-based systems. We have demonstrated
that polyfunctional organometallic precursors such as 2
and 3 are synthetically-available species, and that the
Fig. 2. The X-ray crystal structure of 3, showing the atom numbering
scheme, with thermal ellipsoids at the 30% probability level (solvate
eliminated for clarity).
Fig. 1. The X-ray crystal structure of 2, showing the atom numbering
scheme, with thermal ellipsoids at the 30% probability level (solvate
eliminated for clarity).

104
M. Stradiotto et al. / Journal of Organometallic Chemistry 564 (1998) 101–108
Table 1
Crystal data and structure refinement parameters for 2·CH3CH2OH, 3·H2O, and 4
2·CH3CH2OH
3·H2O
4
Empirical formula
Molecular weight
Colour
C35H32O3P2
562.55
Colourless
Plate
C33H28O1P2S2
566.61
Colourless
Prism
C36H25O3P2S2Mn1
686.56
Yellow
Morphology
Plate
Temperature (K)
Crystal system
Space group
302(2)
Monoclinic
C2/c
35.2038(2)
9.4035(2)
17.2041(2)
90
107.342(1)
90
302(2)
Triclinic
302(2)
Monoclinic
P21/c
12.4768(2)
18.4965(2)
14.3648(3)
90
100.75(1)
90
(
P1
˚
a (A)
9.082(4)
10.073(4)
16.864(5)
89.07(2)
82.96(2)
80.91(1)
1512(1)
2
˚
b (A)
˚
c (A)
h (°)
i (°)
k (°)
3
˚
Volume (A )
Z
5436.3(2)
8
1.375
3256.9(1)
4
1.408
Dcalc. (g cm−3
)
1.245
0.306
v (mm−1
)
0.197
0.667
Scan mode
F(000)
ꢀ-scans
2368
ꢀ-scans
592
ꢀ-scans
1408
q-Range for collection (°)
Index ranges
1.21 to 22.50
−455h545
−115k59
−225l522
15113
3556
3556/0/362
0.866
2.05 to 22.50
−115h511
−125k512
−215l521
10971
3865
3864/0/352
0.921
1.82 to 22.50
−155h515
−225k522
−175l517
18565
4250
4244/0/398
1.019
No. reflections collected
No. independent reflections
Data/restraints/parameters
Goodness-of-fit on F
Final R indices (I\2|(I))a
R1
0.0985
0.2290
0.0568
0.1795
0.0377
0.0787
wR2
R indices (all data)a
R1
0.1391
0.2615
0.979
0.713
0.864
0.0669
0.1902
0.950
0.725
0.937
0.0577
0.0867
0.959
0.677
0.232
wR2
Effective trans. Max.
Effective trans. Min.
Largest difference peak (e A
−3
˚
˚
)
−3
Largest difference hole (e A
)
−0.636
−0.200
−0.214
a R1=ꢀ(ꢁꢁFo−Fcꢁꢁ)/ꢀꢁFoꢁ; wR2=[ꢀ[w(F2o−Fc2)2]/ꢀ[w(Fo2)2]]0.5
.
introduction of a transition metal to the indenyl five-
membered ring is facile. Moreover, the disubstituted
nature of 2 and 3 make them ideal chelating precursors
of heteropolymetallic complexes, which could contain
two or more different metal fragments held together, not
only via a bridging ligand, but also as a result of direct
metal–metal bonding. The utilization of the novel ligands
described herein in the quest for catalytically-synergistic
polymetallic compounds will be the subject of future
reports.
which were previously dried according to standard pro-
cedures. Indene (Aldrich) was distilled prior to use,
diphenylchlorophosphine (Aldrich) was used without
purification and Mn(CO)5Br was prepared using pub-
lished methods [19]. Microanalytical data are from
Guelph Chemical Laboratories, Guelph, Ontario,
Canada. Mass spectra (DEI) were obtained on a VG
Analytical ZAB-SE spectrometer with an accelerating
potential of 8 kV and a resolving power of 10000. All
NMR spectra were acquired on a Bruker Avance
DRX-500 spectrometer, equipped with an 11.74 T su-
perconducting magnet. These experiments consisted of
1D 1H, 13C and 31P NMR spectra as well as 2-D 1H–1H
4. Experimental
1
1
COSY, H–13C shift-correlated and long range H–13C
shift-correlated spectra. All NMR spectra were
recorded on spinning samples (except during the acqui-
sition of 2D spectra), locked to a solvent signal. Proton
4.1. General procedure
All reactions were carried out under an atmosphere
of dry nitrogen in oven-dried glassware using solvents
1
and carbon signals were referenced to a residual H

M. Stradiotto et al. / Journal of Organometallic Chemistry 564 (1998) 101–108
105
signal of the solvent or to a 13C solvent signal, while
phosphorus signals were referenced to external H3PO4.
Table 3
Atomic coordinates (×104) and equivalent isotropic displacement
parameters (A2×103) for 2·CH3CH2OH
Uaeq
4.2. Crystal structure determinations
x
y
z
P(1)
P(2)
O(1)
O(2)
C(1)
C(2)
C(3)
C(3A)
C(4)
C(5)
C(6)
C(7)
C(7A)
C(8)
7347(1)
5959(1)
7315(1)
5807(2)
7131(2)
6724(2)
6472(2)
6700(2)
6585(2)
6863(2)
7251(2)
7367(2)
7094(2)
7087(2)
6860(2)
6646(2)
6654(2)
6886(2)
7101(2)
7842(2)
8022(2)
8414(2)
8637(2)
8458(2)
8067(2)
5772(2)
5961(2)
5797(2)
5455(3)
5264(3)
5424(2)
5838(2)
5928(3)
5831(3)
5630(3)
5535(3)
5633(2)
5666(4)
5489(7)
5360(5)
6749(2)
5066(2)
8215(4)
4384(7)
5586(6)
6036(7)
4991(7)
3715(6)
2351(7)
1351(7)
1699(7)
3060(7)
4095(6)
6447(6)
7493(7)
7317(8)
6084(8)
5012(7)
5186(7)
6225(6)
6349(7)
6200(8)
5837(7)
5699(7)
5895(7)
4311(7)
4433(8)
3888(10)
3181(11)
3086(10)
3623(10)
6895(8)
7753(9)
9146(10)
9661(12)
8841(14)
7428(10)
1955(11)
2455(23)
1401(25)
6146(1)
4490(1)
5880(2)
3705(3)
5297(3)
4942(3)
4892(4)
5182(3)
5214(4)
5515(4)
5793(4)
5751(3)
5447(3)
6862(3)
6990(4)
7525(5)
7907(4)
7790(4)
7260(4)
6579(4)
7375(4)
7688(4)
7190(4)
6398(4)
6083(4)
5247(4)
6041(5)
6591(5)
6340(7)
5545(7)
4998(5)
4441(5)
5089(5)
5019(7)
4301(9)
3654(8)
3709(5)
2866(7)
2078(10)
1626(11)
37(1)
49(1)
44(1)
76(2)
35(1)
39(2)
43(2)
37(2)
49(2)
51(2)
47(2)
40(2)
34(2)
36(1)
53(2)
65(2)
53(2)
52(2)
44(2)
37(1)
45(2)
56(2)
50(2)
51(2)
47(2)
49(2)
63(2)
80(3)
95(3)
91(3)
76(2)
55(2)
69(2)
88(3)
90(3)
96(3)
72(2)
185(5)
215(11)
193(7)
X-ray crystallographic data for 2·CH3CH2OH,
3·H2O and 4 were collected from single crystal sam-
ples, which were mounted on a glass fiber. Data were
collected using a P4 Siemens diffractometer, equipped
with a Siemens SMART 1K charge coupled device
(CCD) area detector (using the program SMART
[20]a) and a rotating anode using graphite-monochro-
˚
mated Mo–Kh radiation (u=0.71073 A). The crystal-
to-detector distance was 3.991 cm, and the data
collection was carried out in 512×512 pixel mode,
utilizing 2×2 pixel binning. The initial unit cell
parameters were determined by a least-squares fit of
the angular settings of the strong reflections, collected
by a 4.5° scan in 15 frames over three different parts
of reciprocal space (45 frames total). One complete
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
O(3)
˚
hemisphere of data was collected, to better than 0.8 A
resolution. Upon completion of the data collection,
the first 50 frames were recollected in order to im-
prove the decay corrections analyses. Processing was
carried out by use of the program SAINT ([20]b),
Table 2
˚
Selected bond lengths (A) and angles (°) for 2·CH3CH2OH, 3·H2O
and 4
1,3-(Ph2P.O)2(C9H6)·CH3CH2OH
P(1)–O(1)
P(2)–O(2)
P(1)–C(1)
P(2)–C(3)
C(1)–C(2)
C(2)–C(3)
1.447(4)
1.445(5)
1.801(6)
1.730(7)
1.446(8)
1.309(8)
O(1)–P(1)–C(14)
O(1)–P(1)–C(8)
O(1)–P(1)–C(1)
O(2)–P(2)–C(3)
O(2)–P(2)–C(20)
O(2)–P(2)–C(26)
112.1(3)
111.6(3)
110.4(3)
114.0(3)
113.1(3)
111.7(4)
C(98)
C(99)
1,3-(Ph2P.S)2(C9H6)·H2O
P(1)–S(1)
P(2)–S(2)
P(1)–C(1)
P(2)–C(3)
C(1)–C(2)
C(2)–C(3)
1.955(1)
1.954(2)
1.855(4)
1.796(4)
1.498(5)
1.332(5)
C(26)–P(1)–S(1)
C(20)–P(1)–S(1
C(1)–P(1)–S(1)
C(3)–P(2)–S(2)
C(14)–P(2)–S(2)
C(8)–P(2)–S(2)
111.8(1)
113.1(1)
110.0(1)
112.3(1)
113.7(2)
113.6(2)
a
Ueq is defined as one third of the trace of the orthogonalized Uij
tensor
which applied Lorentz and polarization corrections to
three-dimensionally integrated diffraction spots. The
program SADABS ([20]c) was utilized for the scaling
of diffraction data, the application of a decay correc-
tion, and an empirical absorption correction based on
redundant reflections. The structure was solved by us-
ing the Patterson method procedure in the Siemens
SHELXTL program library ([20]d), and refined by
full-matrix least-squares methods on F2 with an-
isotropic thermal parameters for all non-hydrogen
atoms. Hydrogen atoms were added as fixed contribu-
tors at calculated positions, with isotropic thermal
parameters based on the carbon atom to which they
are bonded.
(
5-C9H5(Ph2P.S)2[Mn(CO)3]
Mn(1)–C(1)
Mn(1)–C(2)
Mn(1)–C(3)
Mn(1)–C(3A)
Mn(1)–C(7A)
P(1)–S(1)
P(2)–S(2)
P(1)–C(1)
P(2)–C(3)
C(4)–C(5)
C(4)–C(5)
C(5)–C(6)
C(6)–C(7)
2.140(3)
2.117(3)
2.155(3)
2.233(3)
2.237(3)
1.960(1)
1.958(1)
1.819(3)
1.813(3)
1.367(4)
1.367(4)
1.412(5)
1.367(5)
O(32)–C(32)–Mn(1)
O(33)–C(33)–Mn(1)
O(34)–C(34)–Mn(1)
C(33)–Mn(1)–C(2)
C(32)–Mn(1)–C(2)
C(34)–Mn(1)–C(2)
C(33)–Mn(1)–C(1)
C(32)–Mn(1)–C(1)
C(34)–Mn(1)–C(1)
C(33)–Mn(1)–C(3)
C(32)–Mn(1)-C(3)
C(34)–Mn(1)–C(3)
177.9(3)
177.2(3)
177.7(3)
89.0(1)
135.5(1)
132.3(1)
108.1(1)
160.1(1)
95.7(1)
107.3(1)
100.2(1)
155.5(1)

106
M. Stradiotto et al. / Journal of Organometallic Chemistry 564 (1998) 101–108
4.3. Preparations
4.3.1. In situ preparation of 1,3-(Ph2P)2(C9H6), (1)
To a solution of indene (0.93 g, 8.0 mmol) in freshly
distilled diethyl ether (100 ml) at −78°C was added
n-butyllithium (5.0 ml of a 1.6 M hexane solution, 8.0
mmol) over a 1 h period, followed by stirring for an
additional 2 h at −78°C. Diphenylchlorophosphine
(1.77 g, 8.0 mmol) was then added and the mixture
heated under reflux for 3 h. After cooling the mixture
to −78°C, n-butyllithium (5.0 ml of a 1.6 M hexane
solution, 8.0 mmol) was again added over a 1 h period,
followed by the addition of diphenylchlorophosphine
(1.77 g, 8.0 mmol). After refluxing the mixture for 18 h,
stirring was stopped and the solution cooled in order to
allow for the precipitated LiCl to settle. The resulting
Fig. 3. The X-ray crystal structure of 4, showing the atom numbering
scheme, with thermal ellipsoids at the 30% probability level.
Table 4
Atomic coordinates (×104) and equivalent isotropic displacement
parameters (A2×103) for 3·H2O
diethylether solution, containing 1,3-(diphenylphos-
phino)indene was removed from the precipitated LiCl
via cannula then used immediately in the preparation of
2 and 3.
x
y
z
Uaeq
P(1)
P(2)
S(1)
S(2)
C(1)
C(2)
C(3)
C(3A)
C(4)
C(5)
C(6)
C(7A)
C(7)
C(8)
2325(1)
4689(1)
2717(1)
6597(1)
4003(4)
4335(4)
4335(4)
4032(4)
3952(5)
3648(5)
3438(5)
3834(4)
3538(4)
3063(5)
3257(6)
2031(7)
635(7)
6264(1)
7332(1)
4299(1)
7889(2)
6941(3)
6440(4)
7460(4)
8737(3)
4628(1)
1726(1)
4613(1)
1305(1)
4153(2)
3308(2)
2795(2)
3241(2)
2980(2)
3553(3)
4358(2)
4047(2)
4615(2)
1398(2)
753(3)
36(1)
51(1)
50(1)
78(1)
37(1)
42(1)
41(1)
38(1)
50(1)
55(1)
49(1)
36(1)
42(1)
54(1)
71(1)
87(2)
84(2)
78(2)
64(1)
64(1)
103(2)
139(3)
121(3)
119(2)
99(2)
40(1)
55(1)
71(1)
70(1)
61(1)
50(1)
38(1)
54(1)
67(1)
67(1)
66(1)
50(1)
233(5)
4.3.2. 1,3-(Ph2P.O)2(C9H6), (2)
The dioxygen compound, 1,3-(Ph2PO)2(C9H6), 2, was
prepared by bubbling air through a freshly prepared
solution of 1 in diethyl ether for 48 h. After removal of
the solvent, the desired product was isolated as a white
solid by recrystallization from a 50:50 mixture of
CH2Cl2 and 95% ethanol (2.58 g, 5.0 mmol, 63%).
Single crystals suitable for X-ray diffraction studies
(0.28×0.26×0.06 mm) were grown from 95% ethanol
and were found to contain one molecule of ethanol per
10065(4)
11080(4)
10778(4)
8445(3)
9462(3)
8382(4)
9235(5)
10094(6)
10093(6)
9256(6)
8421(5)
5599(5)
4816(6)
3498(8)
2916(7)
3657(7)
5000(6)
6957(4)
6096(4)
6584(6)
7932(6)
8803(5)
8324(4)
6921(3)
6784(4)
7117(5)
7617(5)
7749(5)
7404(4)
3773(7)
C(9)
1
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
O(1)
527(3)
927(3)
asymmetric unit. H NMR (CDCl3, 500 MHz): l 7.62–
7.13 (m, 24H, benzo and phenyl), 6.95 (d of d of d,
442(6)
1554(3)
1800(3)
1496(3)
1076(4)
903(5)
3
3
3JPH=9.1 Hz, JPH=2.4 Hz and JHH=2.0 Hz, 1H,
1632(5)
4576(6)
5759(8)
2
3
H-2), 4.94 (d of d of d, JPH=26.8 Hz, JHH=2.0 Hz
and JPH=1.8 Hz, 1H, H-1). 13C NMR (CDCl3, 125
4
5708(12)
4494(12)
3325(11)
3335(8)
774(4)
MHz): l 144.6 (m, C-2), 143.2–139.8 (C-3, C-3a and
C-7a), 134.0 (d, JPC=20.4 Hz, Ph), 133.7 (d, JPC=20.3
1147(5)
1570(5)
1747(4)
4089(2)
3653(2)
3244(3)
3286(3)
3711(3)
4116(2)
5635(2)
6094(2)
6891(3)
7238(3)
6788(3)
5989(2)
252(7)
Hz, Ph), 132.5 (d, JPC=10.6 Hz, Ph), 132.1 (d, JPC
=
13.5 Hz, Ph), 131.7 (d, JPC=8.4 Hz, Ph), 131.4 (m, Ph),
128.6 (Ph), 128.4 (Ph), 127.9 (C-5), 126.2 (C-6), 125.0
(C-4), 123.4 (C-7), 55.0 (m, C-1). 31P{1H} NMR
(CDCl3, 202 MHz): l 32.0 (PC-1), 22.1 (PC-3). Mass
spectra: (DEI, m/z (%)): 516 (32) ([M]+), 500 (51)
137(5)
−1067(6)
−1650(5)
−1017(5)
185(4)
1953(4)
3139(5)
2882(5)
1453(6)
270(5)
516(4)
9836(8)
a
Ueq is defined as one third of the trace of the orthogonalized Uij
tensor.
Scheme 4. Reaction of the monoanion of 3 with Mn(CO)5Br.

M. Stradiotto et al. / Journal of Organometallic Chemistry 564 (1998) 101–108
107
Table 5
isolated as a yellow powder, m.p. 188–190°C (3.81 g, 7.0
mmol, 87%). Single crystals suitable for X-ray diffrac-
tion studies (0.30×0.22×0.15 mm) were grown from
95% ethanol, and were found to contain one molecule of
water per asymmetric unit. 1H NMR (CDCl3, 500 MHz):
l 7.83–6.86 (m, 24H, benzo and phenyl), 6.42 (d of d of
d, 3JPH=10.1 Hz, 3JPH=3.9 Hz and 3JHH=2.3 Hz, 1H,
Atomic coordinates (×104) and equivalent isotropic displacement
parameters (A2×103) for 4
x
y
z
Uaeq
Mn(1)
P(1)
P(2)
S(1)
S(2)
C(1)
C(2)
C(3)
C(3A)
C(4)
C(5)
C(6)
C(7A)
C(7)
C(8)
1708(1)
2295(1)
1531(1)
782(1)
7539(1)
7613(1)
7297(1)
7120(1)
7333(1)
7154(2)
7601(2)
7058(2)
6211(2)
5411(2)
4697(2)
4745(2)
6263(2)
5501(2)
7359(2)
7043(2)
6875(3)
7030(3)
7341(2)
7498(2)
8897(2)
9424(2)
10391(2)
10831(2)
10323(2)
9358(2)
6369(2)
6014(2)
5329(3)
4990(2)
5334(3)
6021(2)
8408(2)
9265(2)
10116(3)
10134(3)
9310(3)
8447(2)
7446(2)
7467(2)
9628(2)
8813(2)
7497(2)
7444(2)
25(1)
28(1)
25(1)
41(1)
36(1)
25(1)
24(1)
23(1)
25(1)
32(1)
39(1)
39(1)
25(1)
32(1)
29(1)
46(1)
56(1)
53(1)
50(1)
38(1)
31(1)
38(1)
47(1)
49(1)
51(1)
41(1)
29(1)
48(1)
61(1)
57(1)
56(1)
43(1)
30(1)
56(1)
82(2)
84(2)
68(1)
46(1)
50(1)
32(1)
46(1)
31(1)
35(1)
55(1)
−882(1)
3478(1)
−1944(1)
4787(1)
381(3)
1346(3)
2187(3)
1720(3)
2164(3)
1516(3)
423(3)
2
3
H-2), 4.93 (d of d of d, JPH=21.9 Hz, JHH=2.3 Hz
2283(1)
1373(1)
1555(2)
1180(2)
1261(2)
1670(2)
1894(2)
2266(2)
2431(2)
1843(2)
2247(2)
611(2)
4
and JPH=2.1 Hz, 1H, H-1). 13C NMR (CDCl3, 125
MHz): l 143.5 (m, C-2), 143.1–138.2 (C-3, C-3a and
C-7a), 132.4–128.4 (phenyl carbons), 127.9 (C-5), 126.1
(C-6), 124.7 (C-4), 123.8 (C-7), 56.3 (m, C-1). 31P{1H}
NMR (CDCl3, 202 MHz): l 46.9 (PC-1), 32.5 (PC-3).
Mass spectra: (DEI, m/z (%)): 548 (30) ([M]+), 516 (3)
([M–S]+), 331 (13) ([(C9H6)PSPh2]+), 217 (100)
([PSPh2]+); (high resolution, DEI): calculated for mass
608(3)
12
−42(3)
−1389(3)
−782(3)
−1212(3)
−2245(4)
−2858(3)
−2443(3)
−420(3)
54(3)
C H26P2S2, 548.0951 amu; observed, 548.0952 amu.
33
Anal.:Calc. for C33H26P2S2: C 72.25; H 4.78. Found: C
72.31; H 4.71.
C(9)
64(2)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
O(32)
C(32)
O(33)
C(33)
C(34)
O(34)
−628(2)
−783(2)
−247(2)
449(2)
1576(2)
982(2)
1054(2)
1716(2)
2300(2)
2234(2)
94(2)
−207(2)
−747(2)
−988(2)
−694(2)
−151(2)
325(2)
4.3.4. (p5-C9H5(Ph2P=S)2)[Mn(CO)3], (4)
To a solution of 3 (0.69 g, 1.2 mmol) in freshly distilled
tetrahydrofuran (75 ml) at −78°C was added n-butyl-
lithium (0.8 ml of a 1.6 M hexane solution, 1.3 mmol)
over a 1 h period, followed by stirring for an additional
3 h at −78°C. Freshly prepared Mn(CO)5Br (0.34 g, 1.3
mmol) was then added and the mixture heated under
reflux for 12 h. Removal of the solvent yielded a dark
red oil, which was subjected to flash chromatography on
silica gel. Elution with hexane¯CH2Cl2 (70:30) yielded 4
as a yellow solid, m.p. 170–172°C (0.30 g, 0.44 mmol,
37%). Single crystals suitable for X-ray diffraction stud-
ies (0.24×0.18×0.08 mm) were grown from CH2Cl2.
1H NMR (CDCl3, 500 MHz): l 8.44 (m, 2H, H-4/7 or
H-5/6), 7.44–7.14 (m, 20H, phenyl), 7.02 (m, 2H, H-5/6
or H-4/7), 4.07 (m, 1H, H-2). 13C NMR (CDCl3, 125
MHz): l 220.6 (C/O), 131.8–128.6 (phenyl carbons),
128.2 (C-5/6 or C4/7), 125.8 (C-4/7 or C5/6), 108.5 (m,
C-1/3), 101.3 (t, JPC=9.7 Hz, C-2). 31P{1H} NMR
(CDCl3, 202 MHz): l 37.7. Mass spectra: (DEI, m/z
(%)): 686 (2) ([M]+), 602 (32) ([M–3(CO)]+), 217 (100)
([PSPh2]+). Anal. Calc. for C36H25P2S2O3Mn1: C 62.98;
H 3.67. Found: C 62.90; H 3.70.
484(3)
410(3)
−72(3)
−491(3)
3289(3)
2269(3)
2164(4)
3057(4)
4070(4)
4182(3)
3412(3)
3822(4)
3708(5)
3213(5)
2795(4)
2889(3)
3683(2)
2917(3)
2342(2)
2086(3)
863(3)
677(2)
366(3)
−294(3)
−643(2)
−333(2)
3171(1)
2824(2)
2279(1)
2303(2)
3102(2)
3605(1)
305(2)
a Ueq is defined as one third of the trace of the orthogonalized Uij tensor.
([M–O]+), 316 (11) ([(C9H6)POPh2]+), 299 (32)
([(C9H6)PPh2]+), 201 (100) ([POPh2]+) 77 (52)
5. Supplementary material
([C6H5]+); (high resolution, DEI): calculated for mass
X-ray crystallographic data, including complete bond
lengths and angles, anisotropic displacement parameters
and hydrogen atom coordinates for 2·CH3CH2OH,
3·H2O, and 4 (19 pages) are available upon request.
12
C H26P2O2, 516.1408 amu; observed, 516.1412 amu.
33
4.3.3. 1,3-(Ph2P.S)2(C9H6), (3)
The disulfide compound, 1,3-(Ph2PS)2(C9H6) 3, was
prepared by suspending an excess of elemental sulfur in
a
freshly prepared solution of 1,3-(diphenylphos-
Acknowledgements
phino)indene in diethyl ether for 48 h, under nitrogen.
After removal of the residual solid by filtration and
evaporation of the solvent, the desired product was
Financial support from NSERC Canada and from the
Petroleum Research Fund, administered by the Ameri-

108
M. Stradiotto et al. / Journal of Organometallic Chemistry 564 (1998) 101–108
mer, Inorg. Chim. Acta 266 (1997) 19. (c) Z.-G. Fang, T.S.A.
Hor, Y.-S. Wen, L.-K. Liu, T.C.W. Mak, Polyhedron 14 (1995)
2403. (d) K.S. Gan, T.S.A. Hor, in: A. Togni, T. Hayashi
(Eds), Ferrocenes: Homogeneous Catalysis; Organic Synthesis;
Materials Science, chapter 1, VCH, Weinheim, 1995, pp. 3–104.
[7] M. Concepcion, P.G. Jones, A. Laguna, C. Sarroca, J. Chem.
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[8] K.A. Fallis, G.K. Anderson, N.P. Rath, Organometallics 11
(1992) 885.
can Chemical Society, is gratefully acknowledged. MS
thanks NSERC for a postgraduate scholarship. Mass
spectral data were obtained courtesy of Dr Richard
Smith of the McMaster Regional Center for Mass
Spectrometry.
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