Synthesis and structure of two isomers of di(indenyl)phenylphosphine sulfide

Article abstract of DOI:10.1071/C97210

Dichlorophenylphosphine reacts with indenyllithium in tetrahydrofuran followed by sulfur to yield di(1H-inden-3-yl)phenylphosphine sulfide (2). The same reaction sequence in toluene yields di(1H-inden-1-yl)phenylphosphine sulfide (3) as a mixture of (±) a

Full text of DOI:10.1071/C97210

C S I R O P U B L I S H I N G
Australian Journal
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Volume 51, 1998
© CSIRO 1998
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Aust. J. Chem., 1998, 51, 667–672
.
Synthesis and Structure of Two Isomers of
Di(indenyl)phenylphosphine Sul de
Cornelis LensinkA,B and Graeme J. GainsfordA
A
Industrial Research Limited, P.O. Box 31-310, Lower Hutt, New Zealand.
Author to whom correspondence should be addressed.
B
Dichlorophenylphosphine reacts with indenyllithium in tetrahydrofuran followed by sulfur to yield
di(1H-inden-3-yl)phenylphosphine sul de (2). The same reaction sequence in toluene yields di(1H-
inden-1-yl)phenylphosphine sul de (3) as a mixture of ( ) and two meso isomers. The structures
of (2) and ( )-(3) were determined [(2): C24H19PS, Mr 370 42, monoclinic, P 21/n, a 14 329(4),
b 7 0936(10), c 19 405(5) A, 99 18(2) , Z 4, R 0 060 for 2422 observed re ections; (3): C24H19PS,
Mr 370 42, monoclinic, P 21/n, a 9 521(5), b 16 223(8), c 12 930(6) A, 107 41(3) , Z 4, R 0 105
for 923 re ections].
Bruker spectrometer. Solvents were puri ed by conventional
Introduction
methods. Indene and dichlorophenylphosphine (Aldrich) were
used as received. (1H-Inden-1-yl)lithium was prepared by
reaction of butyllithium and indene in hexanes.
The interest in metallocene catalysis with Group
4 ansa-metallocenes as stereospeci c ole n polymeriz-
ation catalysts1,2 and as catalysts for enantioselective
organic transformations3 has resulted in reports of
a number of bridged dicyclopentadienyl compounds.
These ligands consist of two cyclopentadiene fragments
which are connected by a bridge. The bridge can be a
carbon-atom chain of two or more carbon atoms4–8 or
the bridge linking the two cyclopentadiene fragments
can be a single atom. Examples of single-atom bridges
reported thus far contain boron,9 carbon,10 silicon,11
germanium12 and phosphorus.13 Ligands containing
two indenyl or two tetrahydroindenyl fragments are
important for the formation of chiral C2 symmetric
metallocene complexes. There has been a report of
an ansa-bisindenyl ligand with a phosphorus atom
as the single-atom bridge although it was not iso-
lated and characterized.14 Di(cyclopentadienyl)phenyl
phosphine has been reported, as well as the synthesis
of a zirconium and a titanium complex with this
ligand.15,16 We are interested in developing novel
indenyl-containing ligands as part of our work on novel
Group 4 metal catalysis chemistry.17–19 In this paper
we report the synthesis of di(indenyl)phenylphosphine,
a potential Group 4 ansa-ligand with a phosphorus
single-atom bridge, from the reaction of indenyllithium
with dichlorophenylphosphine. A number of di er-
ent isomers were isolated and characterized by n.m.r.
spectroscopy and X-ray crystallography.
Di(1H-inden-3-yl)phenylphosphine (1)
A solution of C6H5PCl2 (1 40 g, 7 8 mmol) dissolved in
tetrahydrofuran (10 ml) was added dropwise to a stirred solu-
tion of LiC9H7 (2 0 g, 16 4 mmol) in tetrahydrofuran (40 ml)
cooled at 78 C. The reaction mixture was allowed to warm
to room temperature and stirred overnight. The solvent was
removed under reduced pressure. Toluene (20 ml) and hexane
(20 ml) were added and the reaction mixture was ltered over
a Celite plug. The toluene/hexane was removed under reduced
pressure to yield (1) as an air-sensitive pale yellow oil (2 44 g,
7 2 mmol, 92%). Attempts to obtain an analytically pure
sample of (1) were not successful. 1H n.m.r. (C6D6) 2 96,
CH2; 6 16, dt, J 3 3, 2 0 Hz, P–C=CH; 6 98, m, 7H; 7 17,
d, J 7 5 Hz, 2H; 7 52, m, 4H. 13C n.m.r. (C6D6) 39 9, d,
J 5 7 Hz; 121 8, d, J 5 3 Hz; 123 9; 125 3; 125 6; 128 7;
128 8; 129 2; 134 4, d, J 129 6 Hz; 140 7, d, J 11 2 Hz;
141 6; 144 3; 146 3, d, J 21 6 Hz. 31P n.m.r. (C6D6) 41 3.
Di(1H-inden-3-yl)phenylphosphine Sul de (2)
A solution of C6H5PCl2 (1 79 g, 10 mmol) dissolved in
tetrahydrofuran (20 ml) was added dropwise to a stirred solu-
tion of LiC9H7 (2 44 g, 20 mmol) in tetrahydrofuran (30 ml)
cooled at 78 C. The reaction mixture was allowed to warm to
room temperature, stirred overnight and then quenched with
a few drops of glacial acetic acid. Freshly sublimed sulfur
(0 32 g, 10 mmol) was added and the reaction mixture stirred
overnight. The solvent was removed under reduced pressure
and the crude product was extracted once with toluene (40 ml).
The product was puri ed by chromatography (silica gel-60;
ethyl acetate/hexanes, 1 : 2) to yield the pure sul de (2) (2 75 g,
7 4 mmol, 74%) (Found: C, 77 5; H, 5 3; S, 8 7. C24H19PS
requires C, 77 8; H, 5 2; S, 8 7%). 1H n.m.r.
(CDCl3)
[n.m.r. assignments are in accord with the numbering shown in
Diagram (A)] 3 56, br, H 3; 6 87, dt, JP–H 10 9, JH–H 1 9 Hz,
2H, H 2; 7 22, m, 4H, H 6/H 7; 7 47, m, 3H, H 12/H 13; 7 49,
m, 2H, H 5; 7 71, m, 2H, H 8; 7 95, dd, J 14 4, 7 9 Hz, 2H,
H 11. 13C n.m.r. (CDCl3) 39 8, d, J 13 9 Hz, C 3; 123 2,
Experimental
General Procedures
All reactions were carried out under an atmosphere of dry
argon or nitrogen. N.m.r. spectra were recorded on an AC300
Manuscript received 5 December 1997
᭧ CSIRO 1998
0004-9425/98/080667$ 05.00

668
C. Lensink and G. J. Gainsford
C 8; 123 9, C 5; 125 7, C 6; 126 5, C 7; 128 6, d, J 13 3 Hz,
C 12; 131 0, d, J 88 2 Hz, C 10; 131 9, d, J 11 4 Hz, C 11;
131 9, d, J 3 3 Hz, C 13; 137 3, d, J 88 4 Hz, C 1; 142 1, d,
J 13 4 Hz, C 9; 144 2, d, J 10 2 Hz, C 4; 146 7, d, J 9 7 Hz,
C 2. 31P n.m.r. (CDCl3) 20 6.
smoothly and produces a high yield of di(1H-inden-3-yl)-
phenylphosphine (1) as is depicted in Scheme 1. It was
not possible to isolate compound (1) because it appears
to be extremely air-sensitive and thermally unstable.
An analogous compound, di(cyclopentadienyl)phenyl
phosphine, was also reported to be very unstable.13,15
Because of this instability compound (1) was fur-
ther puri ed by reacting it with sulfur to form the
corresponding phosphine sul des which are air-stable
compounds (see below). Compound (1) displays one
signal in its 31P n.m.r. spectrum at 41 3 ppm indicat-
Table 1. Crystallographic data and data collection parameters
for (2) and (3)
Di(1H-inden-1-yl)phenylphosphine Sul de (3)
(2)
(3)
A solution of C6H5PCl2 (1 79 g, 10 mmol) dissolved in
toluene (20 ml) was added dropwise to a stirred suspension
of LiC9H7 (2 44 g, 20 mmol) in toluene (30 ml) cooled at
78 C. The reaction mixture was allowed to warm to room
temperature and stirred overnight. The reaction mixture was
quenched with a few drops of glacial acetic acid. Freshly
sublimed sulfur (0 32 g, 10 mmol) was added, the reaction
mixture stirred overnight, ltered and the solvent removed
under reduced pressure. The product was puri ed by chro-
matography (silica gel-60; ethyl acetate/hexanes, 1 : 2) to yield
(3) (3 37 g, 9 1 mmol, 91%) as a mixture of ( ) and two meso
isomers (Found: C, 77 1; H, 5 2; S, 8 5. C24H19PS requires
C, 77 8; H, 5 2; S, 8 7%). Pure ( )-(3) can be obtained by
recrystallization from hot ethanol.
a (A)
b (A)
c (A)
(deg)
Volume (A3)
14 329(4)
7 0936(10)
19 405(5)
99 18(2)
1947 1(8)
42
9 521(5)
16 223(8)
12 930(6)
107 41(3)
1905 7(16)
24
No. of re ections used
for cell determination
range (deg)
4 7–12 5
1 264
0 65 0 3 0 3 0 35 0 1 0 1
pale yellow
0 253
2 13–29 99
0–16
0–9
2 2–8 6
1 291
Dcalc (g/cm3)
Crystal size (mm3)
Crystal colour
orange
0 258
2 07–23 50
0–10
1
Absorption coe cient (mm
collection range (deg)
h range
k range
l range
Re ections collected
Independent re ections
Rint
Absorption (empirical)
max., min. transmission
Number of parameters
Goodness of t on F 2
No. observed data
I > 2 (I)
)
0–18
27–26
14–13
3005
2817
(
)-(3): 1H n.m.r.
(CDCl3) [n.m.r. assignments are in
4549
4284
0 048
accord with the numbering shown in Diagram (B)] 4 81, d,
JP–H 19 7 Hz, P–CH; 4 76, d, JP–H 21 8 Hz, P–CH; 6 40, m,
1H, P–CH–CH=CH; 6 75, m, 1H, P–CH–CH=CH; 7 01, m,
2H, P–CH–CH=CH; 7 25, m, 10H; 7 56, dd, J 12 4, 7 2 Hz,
2H, H 11; 8 02, d, J 6 2 Hz, H 8. 13C n.m.r. (CDCl3) 54 5,
d, J 41 7 Hz, C 1; 55 0, d, 42 2 Hz, C 10; 121 6, C 8; 122 0,
C 80; 124 1, C 5; 124 6, C 50; 125 5, C 6, C 60; 127 4, C 7;
127 6, d, J 5 5 Hz, C 12; 127 9, C 70; 129 5, d, J 5 9 Hz, C 3;
130 6, d, J 5 9 Hz, C 30; 131 4, d, J 8 8 Hz, C 11; 131 7, d,
J 2 Hz, C 13; 135 5, d, J 9 4 Hz, C 2; 135 8, d, J 8 8 Hz,
C 20; 139 5, C 9; 144 6, C 4. 31P n.m.r. (CDCl3) 51 0.
meso-(3) (two isomers): 1H n.m.r. (CDCl3) 4 76, d, JP–H
0 184
0 98, 0 84
311
none
230
0 984
923
1 003
2422
R1 (observed)
wR2
0 060
0 133
0 427
0 227
0 105
0 122
0 338
0 353
3
(max.) (e A
(min.) (e A
)
3
)
20 8 Hz, P–CH. 13C n.m.r.
(CDCl3) 54 8, d, J 42 6 Hz.
31P n.m.r. (CDCl3) 51 2, 52 2.
X-Ray Structure Determination of (2) and (3) (C24H19PS)
Suitable crystals of (2) and (3) were obtained by recrystal-
lization from hot ethanol. Most crystallographic details are
provided in Table 1. Both (2) and (3) have formula weight
370 4 and crystallized with four molecules/cell in the monoclinic
space group P 21/n. The crystals were mounted on a glass
bre under a nitrogen cold stream. All data were collected with
ω scans at 168 K by using graphite-monochromatized Mo K
radiation ( 0 71073 A) on a Siemens P 3 di ractometer.20
The structures were solved by direct methods with SHELXS-
90.21 All non-hydrogen atoms were re ned with anisotropic
displacement parameters. Hydrogen atoms in (2) were located
from di erence Fourier maps and fully re ned. For (3) the
hydrogens were included in idealized positions with xed ther-
mal parameters. Final re nement was done by full-matrix
least-squares re nement with SHELXL-96.22
Results and Discussion
Scheme 1. Synthesis of di(1H-inden-3-yl)phenylphosphine sul-
de (2). (i) LiC9H7, tetrahydrofuran; (ii) 1/8 S8, tetrahydro-
furan; (iii) LiC9H7, toluene; (iv) pyridine.
The reaction of dichlorophenylphosphine with
2 equiv. of indenyllithium in tetrahydrofuran proceeds

Two Isomers of Di(indenyl)phenylphosphine Sul de
669
ing that only one isomer is present. This is consistent
with the proposed structure and is further supported
by the 1H and 13C n.m.r. spectra of (1). The signals
for the protons of the ve-membered ring of the indenyl
moiety appear at 2 96 (CH2) and 6 16 ppm (C=CH).
The latter signal is a doublet of triplets with small
coupling constants of 3 3 and 2 0 Hz (3JP–H and
3JH–H respectively).
consistent with the formation of three isomers. The
racemic ( ) isomer crystallized preferentially when the
crude reaction product was recrystallized from hot
ethanol and this allowed us to assign the ( ) and both
meso signals in the 31P n.m.r. spectrum. ( )-(3) has a
31P n.m.r. chemical shift of 51 0 ppm and the signals at
51 2 and 52 2 ppm were assigned to the two meso-(3)
isomers. In ( )-(3) the two indenyl moieties are not
identical and this results in an almost doubling up of
Compound (1) reacts with 1 equiv. of sulfur to yield
di(1H-inden-3-yl)phenylphosphine sul de (2). This
compound was puri ed by column chromatography on
silica gel. Compound (2) has a 31P n.m.r. chemical
1
all H and 13C n.m.r. signals, most of which could be
1
1
assigned by a combination of H–1H and H–13C COSY
experiments. The 1H and 13C n.m.r. signals of the meso-
(3) compounds were more di cult to assign, mainly
because it was not possible to isolate pure samples of
meso-(3). However, it appears that both isomers have
identical 1H and 13C n.m.r. signals for the more readily
identi ed proton and carbon atoms in the ve-membered
ring of the indenyl moiety (see Experimental).
1
shift of 20 6 ppm, and the H and 13C n.m.r. spectra
are consistent with the proposed structure. The proton
signals of the ve-membered ring appear at 3 56 (CH2)
and 6 87 ppm (C=CH), the latter again as a doublet
3
of triplets with a larger JP–H coupling constant of
10 9 Hz when compared to (1).
When the same reaction sequence was carried out
in toluene instead of tetrahydrofuran, a mixture of iso-
mers of di(1H-inden-1-yl)phenylphosphine sul de (3)
was isolated instead of compound (2). Because the
intermediate phosphine (1), observed as the product
of the reaction in tetrahydrofuran, was found to be
unstable, no attempt was made to isolate or identify the
mixture of intermediate phosphines when the reaction
was carried out in toluene. Instead, the crude product
was converted into the phosphine sul de (3) in a one-pot
synthesis. The phosphorus atom in compound (3) is a
pseudo asymmetric centre. It is not asymmetric when
the carbon atoms directly connected to phosphorus are
both of R (or S) con guration, but it is asymmetric
when one of them is R and the other is S, resulting
in two meso isomers and one racemic ( ) pair (see
Fig. 1).
The existence of meso and ( ) isomers was described
recently for a di(1H-inden-1-yl)dimethylsilane.23 These
silanes undergo interconversion of the meso and ( )
isomers and this could be readily monitored by variable-
temperature n.m.r. experiments. When a pure sample
of ( )-(3), dissolved in CDCl3, was heated at 60 C
for several hours the formation of only a very small
amount of the meso-(3) isomers was observed. The
meso/( ) interconversion of (3) therefore takes place at
a much lower rate than the analogous di(indenyl)silane.
Interestingly, we did observe the appearance of two
new signals at 35 3 and 35 0 ppm, chemical shifts
which are halfway between (2) and (3). We assign
these signals to the two isomers of (1H-inden-1-yl)(1H-
inden-3-yl)phenylphosphine sul de (4). These are the
intermediate products for the complete isomerization
of (3) into (2). Indenyl double-bond rearrangements
of this type are reported to occur only at elevated
temperature23 or by base catalysis.24,25 The addition
of pyridine to an n.m.r. sample of (3) very readily
isomerizes this to (2), while the intermediate signals
assigned to (4) could also be observed. We thus
established that compound (3) readily isomerizes to
the more stable isomer (2) in the presence of a base.
The observed solvent e ect in the synthesis of (2) and
(3) may have its origins in the fact that the use of
tetrahydrofuran is likely to lead to solvent-separated
ion pairs of indenyllithium whereas toluene will lead
to contact ion pairs. This fact may contribute to
a rapid isomerization of (1H-inden-1-yl)phosphine to
(1H-inden-3-yl)phosphine in tetrahydrofuran, catalysed
by indenyllithium, whereas this isomerization does not
take place, or only very slowly, in toluene.
The 31P n.m.r. spectrum of the crude reaction prod-
uct shows three signals at 51 0, 51 2 and 52 2 ppm
Structures of (2) and ( )-(3)
Both compounds (2) and ( )-(3) crystallize from hot
ethanol. Each crystal contains independent molecules
packed with only van der Waals contacts between them:
the closest intermolecular contacts involve indenyl pro-
tons at 2 51 and 2 13 A for (2) and (3) respectively.
Fig. 1. Stereoisomers of di(1H-inden-1-yl)phenylphosphine
sul de (3).

670
C. Lensink and G. J. Gainsford
Table 2. Selected bond distances (A) for (2) and (3)
Table 5. Atomic coordinates and equivalent isotropic displace-
ment parameters (A2) for (2)
Atoms
(2)
C(1)–C(9) C(11)–C(19)
(3)
C(1)–C(9) C(11)–C(19)
Ueq is de ned as one-third of the trace of the orthogonalized
Uij tensor
P(1)–S(1)
P(1)–C(20)
P(1)–C(1)
C(1)–C(2)
C(1)–C(9)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(4)–C(9)
C(5)–C(6)
C(6)–C(7)
C(7)–C(8)
C(8)–C(9)
1 954(1)
1 821(4)
1 934(4)
1 804(10)
Atom
104x
104y
104z
103Ueq
1 786(3)
1 344(5)
1 473(4)
1 500(5)
1 501(5)
1 377(5)
1 403(4)
1 374(6)
1 377(6)
1 386(5)
1 373(5)
1 787(3)
1 332(5)
1 476(4)
1 495(5)
1 502(5)
1 383(5)
1 394(4)
1 376(5)
1 382(5)
1 391(5)
1 387(5)
1 820(10)
1 534(13)
1 463(14)
1 307(13)
1 472(14)
1 381(14)
1 409(13)
1 371(14)
1 365(13)
1 381(13)
1 397(13)
1 831(10)
1 514(13)
1 483(12)
1 305(12)
1 465(13)
1 372(12)
1 414(12)
1 383(13)
1 414(13)
1 383(12)
1 359(12)
S(1)
P(1)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
651(1)
656(1)
12190(1)
9497(1)
8952(4)
7745(5)
7635(6)
8985(5)
9548(5)
10855(6)
11603(7)
11083(6)
9773(4)
8115(4)
6641(5)
5864(6)
7144(5)
7191(6)
8559(6)
9874(6)
9849(5)
8476(4)
8443(5)
6837(6)
6078(7)
6878(7)
8419(7)
9225(6)
8912(1)
8702(1)
7955(2)
7927(2)
7202(2)
6801(2)
6113(2)
5881(2)
6332(2)
7029(2)
7257(2)
9402(2)
9698(2)
10289(2)
10301(2)
10742(2)
10646(2)
10117(2)
9670(2)
9770(2)
8491(2)
8073(2)
7904(2)
8161(2)
8587(3)
8755(2)
43(1)
29(1)
28(1)
38(1)
49(1)
35(1)
45(1)
54(1)
54(1)
43(1)
31(1)
29(1)
35(1)
40(1)
33(1)
42(1)
46(1)
42(1)
37(1)
29(1)
32(1)
49(1)
63(1)
57(1)
55(1)
45(1)
1189(2)
1906(3)
2140(3)
1450(2)
1321(3)
634(3)
81(3)
205(3)
890(2)
1268(2)
912(3)
1601(3)
2438(2)
3298(3)
3947(3)
3751(3)
2889(3)
2235(2)
514(2)
C(7)
C(8)
C(9)
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)
Table 3. Selected bond angles (deg) for (2) and (3)
Atoms
(2) (3)
C(1)–C(9) C(11)–C(19) C(1)–C(9) C(11)–C(19)
651(3)
1543(3)
2294(3)
2145(3)
1261(3)
S(1)–P(1)–C(20)
C(11)–P(1)–C(20)
C(1)–P(1)–C(20)
C(11)–P(1)–S(1)
C(1)–P(1)–S(1)
C(1)–P(1)–C(11)
C(9)–C(1)–C(2)
C(9)–C(1)–P(1)
C(2)–C(1)–P(1)
C(2)–C(3)–C(4)
C(1)–C(2)–C(3)
C(3)–C(4)–C(5)
C(3)–C(4)–C(9)
C(4)–C(5)–C(6)
C(5)–C(6)–C(7)
C(6)–C(7)–C(8)
C(8)–C(9)–C(1)
C(8)–C(9)–C(4)
C(7)–C(8)–C(9)
C(4)–C(9)–C(1)
114 5(1)
105 6(2)
103 1(2)
113 4(1)
113 3(1)
106 1(2)
114 7(4)
108 4(5)
102 5(5)
111 6(4)
114 9(4)
103 7(5)
109 1(3)
108 8(3)
125 6(2)
125 6(3)
102 5(3)
111 6(3)
130 9(5)
109 0(3)
119 2(4)
121 0(4)
120 6(4)
131 1(3)
120 9(3)
118 3(4)
108 0(3)
101 6(9)
102 0(9)
114 4(8)
117 5(8)
110(1)
112(1)
132(1)
107(1)
120(1)
119(1)
120(1)
132(1)
119(1)
121(1)
110(9)
124 2(2)
126 8(3)
103 0(3)
110 9(3)
131 5(3)
108 8(3)
119 4(4)
120 5(4)
121 4(4)
130 7(3)
121 2(3)
117 9(4)
108 1(3)
114 6(8)
110 7(8)
111(1)
111(1)
131(1)
106(1)
117(1)
122(1)
121(1)
132(1)
197(1)
120(1)
111(1)
Table 6. Atomic coordinates and equivalent isotropic displace-
ment parameters (A2) for (3)
Ueq is de ned as one-third of the trace of the orthogonalized
Uij tensor
Atom
104x
104y
104z
103Ueq
Table 4. Selected dihedral angles for (2) and (3)
S(1)
P(1)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
2730(3)
1971(3)
1002(12)
2056(11)
1630(12)
251(13)
635(13)
1902(13)
2291(12)
1424(12)
114(12)
3452(10)
3066(11)
3442(11)
4125(11)
4717(11)
5379(10)
5404(10)
4772(10)
4135(11)
628(11)
54(11)
2914(2)
4023(2)
4233(6)
4175(7)
3601(6)
3219(7)
2625(7)
2417(7)
2782(7)
3388(7)
3622(6)
4789(6)
5661(6)
6192(6)
5766(6)
6052(6)
5506(7)
4659(7)
4382(6)
4916(6)
4306(6)
5104(7)
5298(7)
4720(7)
3920(7)
3714(7)
3547(3)
3510(2)
4500(8)
5657(8)
6205(9)
5543(10)
5793(10)
5003(10)
4007(9)
3758(8)
4531(9)
3821(8)
4050(8)
3422(8)
2697(8)
1919(8)
1387(9)
1642(9)
2412(8)
2943(8)
2250(8)
2071(8)
1104(9)
371(10)
513(8)
49(1)
33(1)
40(3)
45(3)
49(4)
43(3)
51(4)
56(4)
43(3)
43(3)
33(3)
33(3)
35(3)
38(3)
26(3)
38(3)
39(3)
40(3)
33(3)
25(3)
30(3)
42(3)
55(4)
54(4)
54(4)
51(4)
Atoms
(2)
(3)
C(11)–P(1)–C(1)–C(2)
C(20)–P(1)–C(1)–C(2)
S(1)–P(1)–C(1)–C(2)
C(11)–P(1)–C(1)–C(9)
C(20)–P(1)–C(1)–C(9)
S(1)–P(1)–C(1)–C(9)
0 0(4)
110 7(3)
125 0(3)
179 3(3)
68 6(3)
55 7(3)
178 6(3)
1 8(5)
57(1)
170(1)
65(1)
171(1)
76(1)
49(1)
119(1)
64(2)
117(1)
43(1)
65(1)
168(1)
163(1)
54(1)
73(1)
125(1)
55(2)
127(1)
115(1)
136(1)
10(1)
59(1)
50(1)
175(1)
P(1)–C(1)–C(2)–C(3)
P(1)–C(1)–C(9)–C(8)
P(1)–C(1)–C(9)–C(4)
C(1)–P(1)–C(11)–C(12)
C(20)–P(1)–C(11)–C(12)
S(1)–P(1)–C(11)–C(12)
C(1)–P(1)–C(11)–C(19)
C(20)–P(1)–C(11)–C(19)
S(1)–P(1)–C(11)–C(19)
P(1)–C(11)–C(12)–C(13)
P(1)–C(11)–C(19)–C(18)
P(1)–C(11)–C(19)–C(14)
C(1)–P(1)–C(20)–C(25)
C(11)–P(1)–C(20)–C(25)
S(1)–P(1)-C(20)–C(25)
C(1)–P(1)–C(20)–C(21)
C(11)–P(1)–C(20)–C(21)
S(1)–P(1)–C(20)–C(21)
C(7)
C(8)
C(9)
178 5(2)
109 6(3)
0 6(3)
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)
125 5(3)
73 7(3)
177 4(3)
51 3(3)
177 4(3)
1 74(5)
177 2(2)
150 5(3)
98 4(3)
27 0(3)
30 4(3)
80 6(3)
154 0(3)
1021(12)
1522(12)
1056(11)
47(11)
1474(8)

Two Isomers of Di(indenyl)phenylphosphine Sul de
671
Fig. 2. View of the molecular structure of di(1H-inden-3-yl)phenylphosphine sul de (2), with the non-hydrogen atom labelling
scheme. In Figs 2 and 3 the thermal ellipsoids are scaled to 50% probability,26 and the hydrogen atoms have arbitrary radii.
Fig. 3. View of the molecular structure of di(1H-inden-1-yl)phenylphosphine sul de (3), with the non-hydrogen atom labelling
scheme.

672
C. Lensink and G. J. Gainsford
2
Brintzinger, H. H., Fischer, D., Mulhaupt, R., Rieger, B.,
and Waymouth, R. M., Angew. Chem., Int. Ed. Engl., 1995,
34, 1143.
Halterman, R. L., Chem. Rev., 1992, 92, 965.
Roll, W., Zsolnai, L., Huttner, G., and Brintzinger, H. H.,
J. Organomet. Chem., 1987, 322, 65.
Nantz, M. H., Hitchcock, S. R., Sutton, S. C., and
Smith, M. D., Organometallics, 1993, 12, 5012.
Colletti, S. L., and Halterman, R. L., Tetrahedron Lett.,
1989, 30, 3513.
Rieger, B., J. Organomet. Chem., 1992, 428, C3.
Chen, Z. L., and Halterman, R. L., J. Am. Chem. Soc.,
1992, 114, 2276.
Rufanov, K. A., Kotov, V. V., Kazennova, N. B., Lemen-
ovskii, D. A., Avtomonov, A. V., and Lorberth, J.,
J. Organomet. Chem., 1996, 525, 287.
Spaleck, W., Antberg, M., Dolle, V., Klein, R., Rohrmann, J.,
and Winter, A., New J. Chem., 1990, 14, 499.
Herrmann, W. A., Rohrmann, J., Herdtweck, E., Spaleck, W.,
and Winter, A., Angew. Chem., 1989, 101, 1536.
Chen, Y.-X., Rausch, M., and Chien, J. C. W., Organo-
metallics, 1994, 13, 748.
Mathey, F., and Lampin, J.-P., Tetrahedron, 1975, 31, 2685.
Heuer, L., Bode, U. K., Jones, P. G., and Schmutzler, R.,
Z. Naturforsch., 1989, 44b, 1082.
Koepf, H., and Klouras, N., Monatsh. Chem., 1983, 114,
243.
Anderson, G. K., and Lin, M., Inorg. Chim. Acta, 1988,
142, 7.
Gainsford, G. J., and Lensink, C., Acta Crystallogr., Sect. C,
1996, 52, 472.
Lensink, C., Tetrahedron: Asymmetry, 1995, 6, 2033.
Lensink, C., J. Organomet. Chem., 1998, in press.
Fait, J., ‘XSCANS 1.0’, Siemens Analytical Xray Instruments
Division, Nicolet/Siemens Software, 6300 Enterprise Lane,
Madison, Wisconsin, U.S.A., 1993.
Sheldrick, G. M., Acta Crystallogr., Sect. A, 1990, 46, 467.
Sheldrick, G. M., ‘SHELXL-96’, University of Gottingen,
Germany, 1996.
Rigby, S. S., Girard, L., Bain, A. D., and McGlinchey, M. J.,
Organometallics, 1995, 14, 3798.
Friedrich, E. C., and Taggart, D. B., J. Org. Chem., 1975,
40, 720.
Nicolet, P., Sanchez, J.-Y., Benaboura, A., and Abadie,
M. J. M., Synthesis, 1987, 202.
Johnson, C. K., ‘ORTEP II. A Fortran Thermal Ellipsoid
Plot Program for Crystal Structure Illustrations, Report
ORNL5138’, Oak Ridge National Laboratory, Tennessee,
U.S.A., 1976.
A summary of the crystal data, selected bond lengths
and angles, and atomic positional parameters are listed
in Tables 1–6.
The ORTEP diagrams of (2) and
3
4
( )-(3) with the adopted numbering scheme are shown
in Figs 2 and 3.26 For compound ( )-(3) only the
R,R isomer is shown.
5
6
Although the crystals of ( )-(3) were of poorer
quality (several twins were rejected in the prescreen-
ing), the dimensions are self-consistent as shown in
Tables 2–4. Likewise, the inden-3-yl rings in (2) are
identical. Both indenyl geometries are similar to those
reported previously.14 Only the P–S bond length in
( )-(3), at 1 934(4) A, is barely signi cantly smaller
than the P–S bond length of 1 954(1) A in (2) and
in other phosphine sul des (e.g. mean 1 950(2)27 and
1 947(1) A28). The P–C(indenyl) bond lengths (mean
1 787(3) and 1 83(1) A for (2) and (3) respectively) are
signi cantly di erent but both these values lie within
ranges observed previously.29 The phosphorus atom
in (2) has an almost regular tetrahedral geometry as
expected for four-coordinate PV. The angles about
the phosphorus atom range from 103 1(2) for C(20)–
P(1)–C(1) to 113 3(1) for C(1)–P(1)–S(1) with the
bulky sul de atom apparently causing the distortions
from the 109 5 tetrahedral angle. The same pattern
is found for the phosphorus atom in (3) for which
the angles range from 102 5(5) to 114 9(4) . The
indenyl and phenyl rings in (2) are planar with root
mean square deviations of 0 007, 0 010 and 0 008 A
respectively. The phosphorus atom lies just outside
these planes by 0 030(4), 0 089(4) and 0 033(5) A.
Within the poorer structural resolution, the phenyl
and indenyl rings in (3) are also planar. In this case,
the phosphorus is close to planar to the phenyl ring
(0 063(13) A) but 1 488(8) and 1 329(8) A from the
indenyl ring planes.
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
Acknowledgments
The work presented in this paper was funded by
the New Zealand Foundation for Research, Science
and Technology under contract No. CO8403. The
assistance of Dr H. Wong (Industrial Research Ltd)
with the recording of the n.m.r. spectra is appreciated.
27
Zablocka, M., Igau, A., Cenac, N., Donnadieu, B., Dahan, F.,
Majoral, J. P., and Pietrusiewicz, M. K., J. Am. Chem.
Soc., 1995, 117, 8083.
Hayase, S., Erabi, T., and Wada, M., Acta Crystallogr.,
Sect. C, 1994, 50, 1276.
Wilson, A. J. C., (Ed.) ‘International Tables for X-Ray
Crystallography’ Vol. C, Table 9.5.1.1, p. 701 (Kluwer:
London 1992).
28
29
References
1
Wild, F. R. W. P., Wasiucionek, M., Huttner, G., and
Brintzinger, H. H., J. Organomet. Chem., 1985, 228, 63.
Further data (bond lengths and angles, anisotropic displacement parameters, hydrogen atom parameters, and structure factors)
are available, until 31 December 2003, from the Australian Journal of Chemistry, P.O. Box 1139, Collingwood, Vic. 3066.