Oxide, sulfide, selenide, and borane derivatives of indenylphosphines

Article abstract of DOI:10.1071/CH02256

We report the preparation, isolation and characterization of oxide, sulfide, selenide, and borane derivatives of a series of indenylphosphines. Some members of the series had already been prepared, and we have completed the series. We have prepared (inden

Full text of DOI:10.1071/CH02256

CSIRO PUBLISHING
www.publish.csiro.au/journals/ajc
Aust. J. Chem. 2003, 56, 1153–1160
Oxide, Sulfide, Selenide, and Borane Derivatives of
Indenylphosphines
A
A
A,B
A
Julian J. Adams, David E. Berry, Owen J. Curnow,
Glen M. Fern,
A
A
A
Michelle L. Hamilton, Heather J. Kitto and J. Robert Pipal
A
Department of Chemistry, University of Canterbury, Christchurch, New Zealand.
Author to whom correspondence should be addressed (e-mail: o.curnow@chem.canterbury.ac.nz).
B
We report the preparation, isolation and characterization of oxide, sulfide, selenide, and borane derivatives of
a series of indenylphosphines. Some members of the series had already been prepared, and we have com-
pleted the series. We have prepared (indenyl)xPh3−xPO (x = 1–3) for the oxide series, (indenyl)xPh3−xPS (x = 3)
for the sulfides, (indenyl)xPh3−xPSe (x = 1, 2) for the selenides, and (indenyl)xPh3−xPBH3 (x = 1–3) for the
boranes. Linear relationships of the 31P NMR chemical shift with the number of indenyl groups were observed.
1
13
The compounds were also characterized by H and C NMR spectroscopy and mass spectrometry. The solid-
state structure of diindenylphenylphosphine selenide was determined by X-ray crystallography and found to
be isomorphous with diindenylphenylphosphine sulfide. The solid-state structure of triindenylphosphine sulfide
was also determined by X-ray crystallography and the indenyl groups were confirmed to all be the inden-
3
-yl isomer. Additionally, pentacarbonyl(triindenylphosphine)molybdenum(0), 1,3-bis(diphenylphosphino)indene
diborane, and rac-bis(1-(diphenylphosphino)indenyl)iron(ii) diborane were prepared, isolated, and characterized.
Manuscript received: 29 January 2003.
Final version: 19 May 2003.
Introduction
Results and Discussion
Heteropolyfunctional ligands have attracted much interest in
recent years due to their ability to form bi- and poly-metallic
Syntheses
[1]
complexes. These complexes are of particular interest
because of the possibility to introduce two or more metals
with very different electronic and steric properties. This is
usually achieved by a combination of early and late transi-
tion metals. One of the most common systems to be studied is
the cyclopentadienyldiphenylphosphine ligand which is used
extensively in the popular diphosphine chelate bis(diphenyl-
Theseriesofindenylphenylphosphineswithone, two, orthree
indenyl groups have already been prepared (Scheme 1): Fallis
et al. reported indenyldiphenylphosphine (1); Lensink and
[
5]
[
7]
Gainsford reported diindenylphenylphosphine (2); and
[
4]
Heuer et al. reported triindenylphosphine (3). We have also
reported the isolation of 1,3-bis(diphenylphosphino)indene
[
6]
(4). A few of the oxide, sulfide, and selenide derivatives of
these have been reported: Fallis et al. have prepared the sul-
[
2]
phosphino)ferrocene (dppf). Generally, the cyclopenta-
5
[5]
[7]
dienyl functional group is coordinated in an η fashion to one
fide (1b); Lensink and Gainsford, the sulfide (2b); the
only reported derivative of (3) is the platinum complex
metal while the phosphorus atom is coordinated to another
metal. The number of papers reporting indenylphosphine
compounds and their derivatives, in contrast, is very
[4]
Pt(P(C H ) )(PF C H )Cl . Stradiotto et al. reported the
9
7 3
2
9
7
2
[
3a]
and we reported the selenide
oxide (4a) and sulfide (4b)
[3–12]
[6]
[5]
[7]
[3a]
[3a]
small.
This is quite remarkable, given the possibility
(4c). Compounds (1), (2b), (4a),
(4b), and
[
6]
to generate planar chirality at the metal centre containing
the coordinated indenyl ligand and given that indenyl com-
plexes of the group 4 metals have proven especially attractive
(4c) have also been crystallographically characterized. To
fill in the gaps, therefore, we prepared: the oxides (1a),
(2a), and (3a), the sulfide (3b), and the selenides (1c) and
(2c). Additionally, the borane adducts (1d)–(4d), the penta-
carbonylmolybdenum complex (3e), and the borane adduct
[
13–18]
in Ziegler–Natta olefin polmerization.
fide derivates of phosphines are also proving to be of much
interest in homogeneous catalysis.
Oxide and sul-
[
19–22]
ꢀ
In this paper, we
of the ferrocene 1,1 -bis(diphenylphosphinoindenyl)iron(ii)
describe a series of polyfunctional indenylphosphine com-
pounds and the formation of oxide, sulfide, selenide, borane,
and pentacarbonylmolybdenum derivatives.
(5d), were prepared. These compounds were all prepared by
standard methods, namely the oxides either by treatment of
a toluene solution with hydrogen peroxide ((1a) and (3a)) or
©
CSIRO 2003
10.1071/CH02256
0004-9425/03/111153

1
154
O. J. Curnow et al.
E
P
[7]
As with (2b), reported by Lensink and Gainsford, we
found that the oxide (2a) also formed a mixture of the
divinylic, allylic/vinylic, and diallylic isomers in refluxing
toluene (we observed an 8 : 30 : 62 ratio of the isomers,
respectively) starting from the divinylic isomer of the phos-
phine. The diallylic isomer exists as two meso isomers and
one racemic pair, giving a 1 : 2 : 1 ratio in the P NMR spec-
trum at around 38 ppm, whereas the allylic/vinylic isomer
exists as two diastereomers in a 1 : 1 ratio with a P chemical
E
P
Ph
Ph
Ph
E ϭ lone pair (1)
O (1a)
31
E ϭ lone pair (2)
O (2a)
S (1b)
S (2b)
Se (2c)
31
Se (1c)
shift near 27 ppm. The divinylic isomer appears as a singlet
at 17.1 ppm. We did not attempt to separate the isomers. The
selenide and borane adducts were only observed to form the
divinylic isomer.The selenide was heated to reflux in toluene,
so presumably the most stable isomer was formed. We did not
attempt to isomerize the borane adduct, however.
BH (1d)
3
BH (2d)
3
E
P
E
Ph
Ph
Ph
Ph
P
P
E
The NMR studies are consistent with formation of the
trivinylic isomer for all of the triindenylphosphine com-
pounds we prepared: H NMR spectroscopy shows a peak
1
E ϭ lone pair (3)
O (3a)
E ϭ lone pair (4)
O (4a)
around 3.5 ppm with an integral of two protons per indenyl for
S (4b)
Se (4c)
BH3 (4d)
13
S (3b)
Se (3c)
the CH2 group (the corresponding C chemical shift lies at
about 40 ppm) whereas allylic isomers show a peak at around
BH (3d)
3
4
.6 ppmwithanintegralofoneprotonperindenylfortheCHP
Mo(CO) (3e)
5
13
group (the corresponding C chemical shift lies at around
0 ppm). Attempts to isomerize the oxide and sulfide were
BH
3
5
Ph
Ph
unsuccessful. The structure of the sulfide was also confirmed
by X-ray crystallography, which showed that the isolated iso-
P
2
BH
3
mer has the sp carbons attached to the phosphorus in all
Fe
three indenyl rings. This differs from the Pt complex cis-
Pt(P(C9H7)3)(PF2C9H7)Cl2 in which two of the three indenyl
P
Ph
(
5d)
3
[4]
Ph
ringsareattachedviasp carboncentres. Itwasthoughtthat
the formation of a bulkytriindenylphosphine derivative might
give a different isomer, thus the pentacarbonylmolybdenum
adduct was prepared by refluxing hexacarbonylmolybdenum
with triindenylphosphine. Only one isomer was obtained and
this was found by NMR spectroscopy to be the trivinylic
isomer.
By preparing derivatives of 1,3-bis(diphenylphosphino)-
indene (4), we were able to provide examples of phosphorus
in both the allylic and vinylic environments in order to make
direct comparisons. As discussed below, there seems to be
very little affect across the ring.
Scheme 1.
by refluxing a toluene solution of the phosphine in air (2a),
the sulfide (3b) by treatment of a diethyl ether solution of the
phosphine with sulfur), the selenides (1c) and (2c) by heat-
ing a toluene solution to reflux with selenium), the borane
adducts by treatment of the phosphine in dichloromethane
with borane dimethylsulfide), and the pentacarbonylmolyb-
denum complex (3e) by heating a tetrahydrofuran solution of
the phosphine with Mo(CO)6 to reflux.
The compounds have all been characterized by H, 13C,
and 31P NMR spectroscopy. The borane adducts were also
characterized by IR spectroscopy with observation of the
BH3 symmetric and asymmetric stretches at about 2350 and
1
Although many derivatives of dppf are known, prepar-
ing derivatives of the indenyl analogue is more problematic
owing to its increased sensitivity to nucleophilic reagents. We
have recently provided evidence that even the solvent tetrahy-
drofuran is able to reversibly coordinate to the metal centre
−
1
2
390 cm , respectively. EI-MS of all the non-borane com-
[
12]
pounds have also been recorded. Under the conditions of
EI-MS, the borane compounds all show mass spectra con-
sistent with the initial loss of BH3 to form the corresponding
phosphine.
Both the allylic inden-1-yl and vinylic inden-3-yl isomers
of (1) and its sulfide have been observed. For the selenide we
isolated the vinylic isomer, but a small amount of the allylic
isomer, about 10%, was seen in the 31P NMR spectrum of the
product mixture. We observed only the vinylic isomer for the
borane adduct whereas for the oxide we have only observed
the allylic isomer in small amounts during decomposition of
the ferrocenyldiphosphine (5).
and displace the indenide.
Unsurprisingly, therefore, we
have been unable to prepare the oxide and sulfide analogues
of (5) whereas the derivative that contains the electrophilic
fragment BH3 (5d) was readily prepared and isolated. The
Mo(CO)4 adduct, of both the rac and meso isomers, in which
both the phosphorus atoms are coordinated to the Mo atom,
[
6]
has been reported previously.
31P NMR spectroscopy
Table 1 summarizes the 31P{ H} NMR spectroscopy data
for all compounds characterized in this report and compares
these values to some related compounds. For the vinylic
1

Oxide, Sulfide, Selenide, and Borane Derivatives of Indenylphosphines
1155
31
1
Table 1.
P{ H} NMR spectroscopy data for indenylphosphine compounds in CDCl3
1
Compound
Isomer
Phosphine
Oxide
Sulfide
Selenide ( JPSe [Hz])
Borane
Mo(CO)x complex
[
[5]
24]
[30]
[31]
[32]
PPh3
−4.8
29.8
32.7A
23.1
37.5, 37.6, 38.5
27.3, 27.5
17.1
42.6
34.1 (736)
21
37.5
[
5]
PPh2C9H7
1
3
1,1
1
3
−4.3
−22.3
–
45.1
32.1
37.0 (735)
20.8 (721)
–
–
–
–
–
–
–
10.7
–
[
7]
PPh(C9H7)2
51.0, 51.2, 52.2
35.0, 35.3
20.6
,3
,3
–
–
B
−40.3
5.9 (717)
1.2
−8.7
–
[
[
4]
6]
P(C9H7)3
3,3,3
−58.8
10.0
9.6
–
−8.7
[3a]
[3a]
[6]
1
,3-C9H6(PPh2)2
P-1
P-3
−1.1
−21.6
−22.5
32.0
22.1
–
46.9
32.5
–
37.9 (750)
20.9 (730)
–
25.7
11.4
16.5
–
–
[
[
6]
33]
[6]
[38]
(
PPh2C9H7)2Fe
PPh2C9H6)2Fe
33.1
[34]
[35]
[36]
[37]
(
−17.2
28.3
40.8
31.5 (737)
16.5
28.5
A
B
Minor product observed in the decomposition of (5).
Our measurement.
6
0
isomers, there is an upfield shift, αE, upon replacement
of a phenyl group with an inden-3-yl group. The magni-
tude of this upfield shift is strongly dependent upon the
nature of the phosphine adduct), thus, the phosphines give
an upfield shift of 18.0 ppm for each substitution of a phenyl
by an inden-3-yl, whereas the oxides give an upfield shift
of 6.3 ppm per substitution. Figure 1 illustrates the trends
observed for the chemical shifts of the phosphines and
their oxide, sulfide, selenide, and borane derivatives. A sim-
ple equation for indenylphenylphosphine adducts can be
derived in which the chemical shift δ is dependent on αE,
the chemical shift of triphenylphosphine as free species ver-
sus as an adduct ∆E, and the number of indenyl groups, x:
δ = ∆E + ꢀxαE − 4.8. Table 2 tabulates the αE and ∆E val-
ues for the indenyl phosphines we describe here as well as
methyl-, ethyl-, and isopropylphenylphosphines and some of
their adducts. One consequence of these different αE val-
ues is that whereas triphenylphosphine oxide (28.5 ppm) is
upfield of the selenide (34.1 ppm) and the molybdenum-
pentacarbonyl adduct (37.5 ppm), the order is reversed for
the triindenylphosphine adducts (10.0 ppm for the oxide ver-
sus −7.2 ppm (calculated) and −8.7 ppm for the selenide and
molybdenumpentacarbonyl adducts, respectively).
40
20
0
Ϫ20
Ϫ40
Ϫ60
Ϫ80
phosphine
oxide
sulfide
selenide
borane
0
1
2
3
Number of indenyl substituents
Fig. 1. 31P NMR chemical shifts of indenylphenylphoshines (C9H7)x-
Ph3−xP (x = 0–3), and their oxide, sulfide, selenide, and borane adducts.
Table 2. 31P NMR chemical shift parameters for substituted
phenylphosphines RxPh3−xP (x = 0–3) and their adducts
Based on the formula δ = ∆E + ꢀxαE − 4.8
The upfield shift from triindenylphosphine oxide to the
sulfide (10.0 versus 9.6 ppm, respectively) goes against con-
ventional wisdom, which says that ‘in tetravalent and penta-
valent phosphorus compounds the transition from oxygen to
sulfur is accompanied in every case by a large downfield
E
∆E
αE
αE
αE
αE
αE
αE
i
(Ph) (3-indenyl) (1-indenyl) (Me) (Et) (Pr )
Lone pair 0.0
0
0
0
0
0
0
−18.0
−6.3
2
4
5
4
5
–
−19.1 −5.1 8.1
O
S
Se
BH3
34.6
49.4
39.0
25.8
2.1
4.8
6.2
3.3
[23]
shift of around 30–80 ppm’.
The diindenylphenylphos-
−11.0
−14.1
−9.9
phine adducts show only a small downfield shift of 3.5 ppm.
Selenide chemical shifts are generally very similar to the
Mo(CO)5 42.5
−15.4
[24]
sulfides,
so the 15 ppm upfield shift from the diindenyl-
phenylphosphine sulfide to the selenide would be considered
large.
Substitution of a phenyl group by an inden-1-yl group
results in a small downfield shift of less than 6 ppm for all of
the compounds we have prepared. Comparison of inden-1-
and inden-3-yldiphenylphoshine and its adducts with 1,3-
bis(diphenylphosphino)indene and its adducts shows little
difference (less than 4 ppm) across the indene ring upon
substitution of a proton by a diphenylphosphino group.
Thus, comparison of triphenylphosphine and its adducts
with the chemical shift of the 1-diphenylphosphino group
in 1,3-bis(diphenylphosphino)indene allows us to determine
a consistent set of α values for the inden-1-yl group. As
E
shown in Table 2, the α values for inden-1-yl (3 ± 2) do not
E
vary much, in contrast to the α values for inden-3-yl (which
E
range from −6.3 to −18.0), and are remarkably similar to
phenyl (0, by definition).

1
156
O. J. Curnow et al.
1
1
Grim and McFarlane developed the equation δ = −62 +
H2 and H7 followed by a combination of H– H COSY and
P
P
[25]
31
1
13
ꢀ
σ (based on σ (Me) = 0)
for calculating the P chem-
H– C HSQC spectroscopy of compound (2b), since this
1
ical shifts of tertiary phosphines. Using this equation, we can
compound has well-separated H resonances for H4–H7.The
assignment of the quaternary carbons C3, C3a, C7a, and ipso-
Ph is based on their chemical shifts and coupling constants
P
P
P
calculate that σ (inden-3-yl) = 1, σ (inden-1-yl) = 19, σ
P
(
C5H5Fe(C5H4PPh2)) = 7, andσ (C9H6Fe(C9H6PPh2)) = 2.
P
P
1
13
In comparison, σ (Ph) = 19 and σ (pentyl) = 10. Thus, the
inden-3-yl resembles a methyl group and the inden-1-yl
again resembles a phenyl group. This is opposite to what
one might expect and suggests that the inden-3-yl group is
a significantly better π-donor than phenyl. Schmidpeter and
and was confirmed by use of H– C HMBC spectroscopy.
The chemical shift of C7a varies by less than 1.5 ppm whereas
C3a, being closer to the point of modification, has a much
greater variation of 5 ppm (10 ppm if (3a) is included).
With the peculiar exception of triindenylphosphine oxide,
a number of trends can be observed: The variation in chem-
ical shift decreases as the number of bonds from the P atom
increases), for C3 (one bond), the chemical shifts have a
range of ± 7 ppm, for C2 (two bonds) ± 3.6 ppm, for C3a (two
bonds) ± 2.5 ppm, for C1 (three bonds) ± 0.3 ppm, and for
C7a (three bonds) ± 0.6 ppm. The magnitude of the coupling
constants generally decrease C3 > C1 = C3a > C2 = C7a >
C4. The phosphines have smaller coupling constants (except
for C4) than the derivatives.
[26]
Brecht
used the equation δ = 39.6 + 22.7σX to describe
3
1
the P chemical shifts for phosphine oxides of the for-
mula Ph2P(O)X, where σX is the para-Hammett constant.
We find that σX (inden-1-yl) = −0.304 and σX (inden-3-yl) =
−
0.727. These compare to −0.43 for phenyl, −0.52 for
−
pentyl, −0.660 for NH2, and −1.00 for O .Again, the inden-
1
-ylmostcloselyresemblesaphenylgroupandtheinden-3-yl
most closely resembles a π-donor group.
The ferrocenyldiphosphine (5) and its adducts show sim-
ilar chemical shifts to the cyclopentadienyl analogues. The
dppf derivatives are between 5 and 11 ppm downfield of the
corresponding indenyldiphenylphosphine adduct.
As expected, C4 has a small, at most 5 Hz, coupling con-
stant to phosphorus compared with that of C1 and C7a since
it is observed that in general JPC-trans is much larger and
3
3
[27]
JPC-cis.
Two-bond coupling constants of phosphines tend
to depend on the orientation of the phosphine lone pair (the
coupling constant is larger for the atom it is closest to, so,
generally, C3a > C2). Thus, it might be expected that, for the
other derivatives, the coupling constant would also depend
on the orientation of the phosphine substituent.
The chemical shifts and coupling constants of C3 and
C3a of triindenylphosphine oxide are out of line with the
above trends. The one bond coupling constant to C3 is only
10 Hz, versus over 100 Hz for the monoindenyl and diindenyl
oxides, while the chemical shifts of C3 and C3a are signif-
icantly upfield of the other compounds: 128.8 ppm versus
1
3
1
C{ H} NMR Spectroscopy
Table 3 summarizes the 13C{ H} NMR spectroscopy for the
indenyl rings of the indenyl compounds discussed in this
report. The assignments of C1 and C2 are obvious from their
chemical shifts. C4 is also easily assigned since it is often a
doubletorisatleastbroadenedbycouplingtoP.Thepatternof
resonances for C4 to C7 is well dispersed and invariant from
one compound to another with each resonance varying by a
range of less than 1.5 ppm.The assignments of C4 to C7 were
confirmed by the observation of an NOE effect from H1 to
1
13
1
Table 3.
C{ H} NMR spectroscopy data for indenyl phosphine derivatives
JPC [Hz] data in parentheses
7
1
7
a
a
6
5
2
3
3
4
PR
2
C1
C2
C3
ipso-Ph
136.0(9)
C3a
C4
C5
C6
C7
C7a
[
5]
(
(
(
(
(
(
(
(
(
(
(
(
(
(
C9H7)PPh
40.2(6)
142.0(6)
145.9(20)
141.9(13) 121.5(5) 126.4 125.3 124.1 144.8(5)
2
C9H7)PPh2O
C9H7)PPh2Se
C9H7)PPh2BH3
C9H7)2PPh
C9H7)2PPhO
C9H7)2PPhS
C9H7)2PPhSe
C9H7)2PPhBH3
C9H7)3PA
40.1(14) 148.8(10) 138.2(106) 131.7(106) 142.4(12) 122.6
126.6 125.6 123.8 143.8(10)
126.3 125.6 123.9 144.2(10)
126.5 125.6 122.9 144.1(8)
39.8(13) 147.0(9)
40.2(11) 148.6(8)
136.8(78)
134.5(57)
145.8(21)
130.3(77)
128.1(59)
133.8(5)
141.7(13) 123.2
142.7(11) 122.9
39.9(4)
141.7(4)
139.9(10) 121.3(5) 126.2 124.9 123.6 144.1(5)
39.9(14) 147.8(12) 137.7(109) n. o.
39.8(14) 146.7(10) 137.3(88) 131.0(88)
142.3(12) 122.5
142.1(13) 123.2
126.5 125.5 123.7 143.7(8)
126.5 125.7 123.9 144.2(10)
126.4 125.7 124.0 144.2(10)
126.5 125.6 123.9 144.1(8)
[7]
39.8(14) 146.8(8)
40.3(11) 148.1(8)
135.6(80)
133.5(59)
146.1(22)
129.0(120) 141.9(14) 123.2
127.3(60)
142.9(12) 122.9
40.2(4)
142.4(4)
138.1(8)
133.0(9)
121.6(5) 126.5 125.1 123.9 144.3(5)
122.7
C9H7)3P
C9H7)3P
O
S
40.1(14) 147.4(11) 128.8(10)
39.8(15) 147.0(10) 136.2(90)
126.6 125.6 123.8 143.8(10)
126.5 125.6 123.9 144.1(12)
126.5 125.5 123.8 144.0(8)
125.9 125.3 123.9 144.3(7)
142.0(12) 123.0
142.9(12) 122.8
143.1(11) 122.9
C9H7)3PBH3
C9H7)3PMo(CO)5
40.2(11) 147.8(7)
132.3(59)
39.7(10) 145.4(11) 136.5(37)
A
[4]
Our assignment of the spectrum reported by Heuer et al.

Oxide, Sulfide, Selenide, and Borane Derivatives of Indenylphosphines
1157
◦
C(23)
Table 4. Selected bond lengths [Å] and angles [ ] for diindenyl-
C(24)
C(12)
C(14)
C(13)
C(11)
phenylphosphine selenide (2c) and triindenylphosphine sulfide (3b)
Se
C(19)
C(15)
(2c)
(3b)
C(22)
C(21)
C(18) C(10)
C(17)
Se–P
2.1190(14)
1.787(5)
1.791(5)
1.808(5)
P–S
1.946(2)
1.781(6)
1.787(5)
1.773(6)
C(16)
P
P–C(13)
P–C(23)
P–C(31)
P–C(13)
P–C(23)
P–C(33)
C(20)
C(1)
C(9)
C(13)–P–Se
C(23)–P–Se
C(31)–P–Se
C(13)–P–C(23)
C(13)–P–C(31)
C(23)–P–C(31)
113.21(18)
112.99(18)
114.15(18)
105.8(2)
104.5(2)
105.4(2)
C(13)–P–S
C(23)–P–S
C(33)–P–S
113.48(19)
110.3(2)
113.99(19)
106.8(2)
105.4(3)
106.3(3)
C(2)
C(8)
C(7)
C(23)–P–C(13)
C(33)–P–C(13)
C(33)–P–C(23)
C(3)
C(4)
C(5)
C(6)
◦
Table 5. Selected dihedral angles [ ] for diindenylphenylphos-
[
7]
Fig. 2. Thermal ellipsoid plot (40%) of diindenylphenylphosphine
selenide (2c) showing the atomic labelling scheme.
phine sulfide (2b), diindenylphenylphosphine selenide (2c),
and triindenylphosphine sulfide (3b)
(
(
(
2b)
2c)
3b)
S–P–C1–C9
S–P–C11–C19
55.7(3)
51.3(3)
27.0(3)
52.8(5)
50.7(5)
37.2(5)
53.1(5)
49.5(5)
−168.2(4)
C(12)
C(33)
S
P
C(32)
C(31)
C(13)
C(14)
S–P–C20–C25 (Ph)
Se–P–C13–C13A
Se–P–C23–C23A
Se–P–C31–C36 (Ph)
S–P–C23–C23A
S–P–C33–C33A
S–P–C13–C13A
C(35) C(34)
C(11)
C(19)
C(39)
C(38)
C(15)
C(16)
C(17)
C(28)
C(27)
C(36)
C(18)
C(37)
C(21)
C(29)
C(22)
1
39 ± 7 ppm for C3 and 133.0 ppm versus 140.6 ± 2.5 ppm
for C3a. We cannot readily account for these observations.
C(23)
C(24)
C(25)
C(26)
Structures of Diindenylphenylphosphine Selenide (2c)
and Triindenylphosphine Sulfide (3b)
Fig. 3. Thermal ellipsoid plot (40%) of triindenylphosphine sulfide
Table 4 lists selected bond distances and angles for diindenyl-
phenylphosphine selenide (2c) and triindenylphosphine sul-
fide (3b). Selected dihedral angles for the two compounds,
as well as for (2b), are given in Table 5. For both compounds
there are no anomalies in the structural parameters and there
is good self-consistency in the indenyl ligands.
(3b) showing the atomic labelling scheme.
Conclusion
We have described the completion of a series of indenyl-
phenylphosphines and their oxide, sulfide, selenide, and
borane adducts. Trends in their 31P and C NMR spectra
have been observed and it was found that inden-1-yl groups
appear to behave similarly to phenyl groups whereas the
inden-3-yl groups are much more variable in their affects,
presumably due to π-donor effects. The X-ray structures of
triindenylphosphine sulfide and diindenylphenylphosphine
selenide were much as expected with both adopting propeller
conformations.
13
The solid-state structure of (2c), illustrated in Figure 2, is
isomorphous to that of the sulfide (2b): It has the same space
[7]
group, P21/n, and similar cell dimensions. As shown in
Table 5, the orientations of the indenyl and phenyl rings are
essentially the same: The benzo rings are oriented towards
the selenium atom and the three rings adopt a propeller con-
formation. The Se–P–C angles are slightly smaller than for
◦
◦
◦
◦
the sulfide: 113.2 and 113.0 versus 113.4 and 113.3 for
◦
◦
the indenyl rings and 114.2 versus 114.5 for the phenyl
ring. This is consistent with the decreased electronegativity
of Se versus S, rather than a steric effect. The P–Se distance
of 2.1190(14) Å is indistinguishable from the P–Se distances
in (4c): 2.1251(14) and 2.1265(14) Å for the phosphorus on
Experimental
All manipulations and reactions were carried out under an inert
atmosphere (Ar or N2) by use of standard Schlenk line tech-
niques. Reagent grade solvents were dried and distilled prior
to use: diethyl ether and tetrahydrofuran from Na/benzophenone;
2
◦
the sp carbon atom and 2.1144(14) and 2.1138(15) Å for the
phosphorus on the sp carbon atom.
dichloromethane and petroleum ether (50–70 C fraction) from CaH2.
3
[6]
[5]
[6]
Indenyldiphenylphosphine, 1,3-bis(diphenylphosphino)indene, and
5
[6]
bis(1-(diphenylphosphino)-η -indenyl)iron(ii) were prepared by pub-
The conformation adopted by (3b) in the solid state, illus-
trated in Figure 3, is also a propeller conformation but with
two of the benzo rings oriented towards the S atom and the
third oriented away from the S atom.
lished procedures. All other reagents were purchased from Aldrich
or Sigma. 1H, C{ H}, and P{ H} NMR spectroscopy data were
13
1
31
1
collected on either a Varian XL- or UNITY-300 spectrometer oper-
ating at 300, 75, and 121 MHz respectively. NOE, 1H– H COSY,
1

1
158
O. J. Curnow et al.
1H–13C HSQC, and H– C HMBC spectra were collected on a Varian
1
13
To a solution of indene (2.2 g, 2.0 mmol) in diethyl ether (25 mL)
1
13
◦
n
INOVA-500 spectrometer operating at 500 and 125 M for H and C,
respectively. Spectraweremeasuredatambienttemperaturewithresidue
solvent peaks as internal standard for H and C{ H} NMR spectro-
scopy. P{ H} NMR spectroscopy chemical shifts were reported
relative to external 85% H3PO4, positive shifts representing deshielding.
EI mass spectra were collected on a Kratos MS80RFA mass spectro-
meter. Infrared spectra were obtained on a Shimadzu FTIR-8201PC
spectrophotometer. Elemental analysis was done by Campbell Micro-
analytical Services, Otago University, Dunedin. Yields have not been
optimized.
at −78 C was added a solution of Bu Li (12.5 mL, 1.6 M, 2.0 mmol).
After stirring the reaction mixture at ambient temperature for 1 h, the
1
13
1
◦
solution was again cooled to −78 C. PhPCl2 (1.8 g, 1.0 mmol) was
3
1
1
then added and the solution then stirred at ambient temperature for 1 h
before filtration through an alumina column (10 × 1.5 cm). The solvent
was removed in vacuo and the residue washed with methanol to give
diindenylphenylphosphine (2) (2.5 g, 74%) as a cream powder. (Found:
C 83.03, H 5.53%. C24H19P requires C 85.19, H 5.66%). δH (CDCl3)
7.5–7.1 (13 H, m, H4–H7, Ph-H), 6.27 (2 H, s, H2), 3.38 (4 H, s, H1).
1
3
δC{H} (CDCl3) 145.76 (d, JPC 21, C3), 144.14 (d, JPC 5, C7a), 141.65
2
2
2
(
d, JPC 4, C2), 139.91 (d, JPC 10, C3a), 134.05 (d, JPC 20, ortho-
Ph), 133.78 (d, J 5, ipso-Ph), 129.07 (s, para-Ph), 128.47 (d, J
PC PC
1
3
Preparation of Indenyldiphenylphosphine Oxide (1a)
8
, meta-Ph), 126.22 (s, C5), 124.87 (s, C6), 123.62 (s, C7), 121.33 (d,
To a solution of indenyldiphenylphosphine (2.53 g, 8.4 mmol) in toluene
3
3
JPC 5, C4), 39.87 (d, JPC 4, C1). δP{H} (CDCl3)−40.33.
(
5
50 mL) was added an excess of aqueous hydrogen peroxide (2 mL,
0% w/w). The reaction mixture was stirred at ambient tempera-
Preparation of Diindenylphenylphosphine Oxide (2a)
ture for 12 h. After filtering, the solvent was removed in vacuo to
leave a yellow oily residue. Recrystallization (diethyl ether) afforded
indenyldiphenylphosphine oxide (1a) (0.93 g, 35%) as a yellow pow-
Diindenylphenylphosphine (0.4 g, 1.2 mmol) was dissolved in freshly
distilled toluene (25 mL) and heated in air to reflux for 4 h. Removal of
solvent in vacuo gave an isomeric mixture of diindenylphenylphosphine
oxide (2a) as a yellow oil, which could not be crystallized. Microanal-
ysis was not attempted due to the oily nature of the mixture. (Found:
+
•
+•
der. (Found: M 316.10186. C21H17OP requires M 316.10170).
δH (CDCl3) 7.8–6.8 (15 H, m, H2, H4–H7, and Ph), 3.57 (2 H, s, H3).
2
3
δC{H} (CDCl3) 148.8 (d, JPC 10, C2), 143.8 (d, JPC 10, C7a), 142.4
2
1
4
+•
+•
−1
(
d, JPC 12, C3a), 138.2 (d, JPC 106, C3), 132.0 (d, JPC 3, para-Ph),
M
354.11709. C24H19OP requires M 354.11735). ν/cm (Nujol)
1
2
1
31.7 (d, JPC 106, ipso-Ph), 131.6 (d, JPC 10, ortho-Ph), 128.5 (d,
JPC 12, meta-Ph), 126.6 (s, C5), 125.6 (s, C6), 123.8 (s, C7), 122.6 (s,
2225 w, 1590 m, 1549 w, 1450 s, 1377 s, 1260 s, 1233 w, 1178 w,
1150 m, 1100 m, 1020 m, 957 w, 907 m, 799 s, 762 s, 721 s, 694 s,
644 m, 603 m, 567 m, 519 m. δH (CDCl ) 7.9–6.5 (15 H, m), 3.48 (4 H,
s, H1). δ
3
3
C4), 40.1 (d, JPC 14, C1). δP{H} (CDCl3) 23.85. m/z (EI) 316 (47%,
3
+
+
+
+
2
3
M ), 201 (100, [M–C9H7] ), 115 (26, C9H ), 77 (30, C6H ).
3 PC PC
(CDCl ) 147.8 (d, J 12, C2), 143.7 (d, J 8, C7a),
42.3 (d, JPC 12, C3a), 137.7 (d, JPC 109, C3), 132.0 (d, JPC 3, para-
7
5
C{H}
2
1
4
1
2
3
Preparation of Indenyldiphenylphosphine Selenide (1c)
PC PC
Ph), 131.2 (d, J 10, ortho-Ph), 128.4 (d, J 12, meta-Ph), 126.5 (s,
C5), 125.5 (s, C6), 123.7 (s, C7), 122.5 (s, C4), 39.9 (d, JPC 14, C1).
No ipso-Ph carbon atoms were observed. Peaks corresponding to C1 of
3
To a solution of indenyldiphenylphosphine (0.40 g, 1.33 mmol) in
tetrahydrofuran(30 mL)wasaddedseleniumpowder(0.16 g, 2.0 mmol).
The reaction mixture was stirred at ambient temperature for 16 h. After
filtering through Celite, the solvent was removed in vacuo to afford
indenyldiphenylphosphine selenide (1c) (0.47 g, 93%) as a white pow-
1
the allylic/vinylic isomers were also observed: 52.4 (d, JPC 64), 53.0
1
(
d, JPC 64). δP{H} (CDCl3) 38.50 (2%, s), 37.65 (4%, s), 37.50 (2%,
s), 27.52 (15%, s), 27.28 (15%, s), 17.08 (62%, s). m/z (EI) 354 (82%,
+ +
+
+
+
•
+•
M ), 239 (90, [M–C H ] ), 192 (42, PhC H ), 115 (100, C H ).
der. (Found: M 380.02262. C21H17PSe requires M 380.02331).
δH (CDCl3) 7.9–6.6 (15 H, m, H2, H4–H7, Ph), 3.58 (2 H, s, H3). δC{H}
9 7 9 9
7
7
2
3
2
Preparation of Diindenylphenylphosphine Selenide (2c)
(
CDCl3) 147.0 (d, JPC 9, C2), 144.2 (d, JPC 10, C7a), 141.7 (d, JPC
3, C3a), 136.8 (d, JPC 78, C3), 132.4 (d, JPC 11, ortho-Ph), 131.7 (d,
JPC 3, para-Ph), 130.3 (d, JPC 77, ipso-Ph), 128.6 (d, JPC 12, meta-
1
2
1
Diindenylphenylphosphine (0.4 g, 1.2 mmol) was dissolved in freshly
distilled toluene (25 mL). Powdered selenium (89 mg, 1.1 mmol) was
added and the mixture heated to reflux for 1.5 h. The solvent was
removed in vacuo from the clear yellow solution. Recrystalliza-
tion (toluene/hexane) afforded diindenylphenylphosphine selenide (2c)
(0.20 g, 46%) as light-brown crystals. (Found: C 69.70, H 4.74%.
4
1
3
Ph), 126.3 (s, C5), 125.6 (s, C6), 123.9 (s, C7), 123.2 (s, C4), 39.8 (d,
3
JPC 13, C1). δP{H} (CDCl3) 20.79 (m, JPSe 721). m/z (EI) 380 (20%,
+
+
+
+
M ), 300 (77, [M–Se] ), 265 (53, Ph2PSe ), 185 (100, Ph2P ), 115
+
+
24, C9H ), 77 (24, Ph ).
7
(
−
1
C24H19PSe requires C 69.07, H 4.59%). ν/cm (Nujol) 1278 m, 1261
m, 1234 m, 1195 w, 1180 w, 1165 w, 1096 s, 1018 m, 995 w, 955 s, 920
w, 805 w (P = Se), 775 m, 760 s, 748 s, 735 s, 716 s, 691 s, 635 s, 602
Preparation of Indenyldiphenylphosphine Borane (1d)
Indenyldiphenylphosphine(1.00 g, 3.3 mmol)wasdissolvedindichloro-
−
1
H 3
s. δ (CDCl ) 7.96 (2 H, dd, J 8, 14, ortho-Ph), 7.73 (2 H, m, H4), 7.46
methane (50 mL). Borane dimethylsulfide (2 mL, 2 mol L , 4.0 mmol)
was added and the reaction mixture stirred overnight. The solvent was
removed in vacuo and a recrystallization carried out with dichloro-
methane and petroleum ether. A second recrystallization was carried
out with hot ethanol to give indenyldiphenylphosphine borane (1d)
(
5 H, m, H7, para-Ph, meta-Ph), 7.20 (4 H, m, H5, H6), 6.86 (2 H, d,
JPH 11, H2), 3.56 (4 H, s, H1). δC{H} (CDCl3) 146.82 (d, JPC 8, C2),
3
2
44.19 (d, 3JPC 10, C7a), 141.87 (d, JPC 14, C3a), 135.56 (d, 1JPC
2
1
8
1
0, C3), 132.40 (d, JPC 11, ortho-Ph), 131.94 (d, 4JPC 3, para-Ph),
2
3
1
28.68 (d, JPC 13, meta-Ph), 129.01 (d, JPC 120, ipso-Ph), 126.44 (s,
(
0.757 g, 72%) as a light-yellow powder. (Found: C 78.68, H 6.41%.
3
−
1
C5), 125.71 (s, C6), 123.98 (s, C7), 123.20 (s, C4), 39.78 (d, J 14,
C21H20BP requires C 80.28, H 6.42%). ν/cm (KBr) 3057 s, 2390
vs, 2345 ms, 1458 s, 1437 vs, 1059 vs, 739 vs, 694 vs, 608 s, 488 s.
δH (CDCl3) 7.70 (5 H, m, H4, ortho-Ph), 7.46 (5 H, m, H7, meta-Ph),
7
3
8
5
(
(
1
PC
+
C1). δP{H} (CDCl3) 5.94 (m, JPSe 717). m/z (EI) 418 (46%, M ), 338
+
+
+
(
37, [M–Se] ), 303 (55, [M–C9H7] ), 223 (69, PhPC9H ), 192 (42,
7
3
3
+ +
+
PhC9H ), 191 (42, PhC9H ), 145 (33, C9H6P ), 115 (100, C9H ).
7 6
+
.19 (4 H, m, H5, H6, para-Ph), 6.80 (1 H, dt, JPH 8.7, JHH 2, H2),
7
2
.57 (2 H, d, J 2, H1), 1.3 (3 H, m, BH3). δC{H} (CDCl3) 148.6 (d, JPC
3
2
1
, C2), 144.1 (d, JPC 8, C7a), 142.7 (d, JPC 11, C3a), 134.5 (d, JPC
Preparation of Diindenylphenylphosphine Borane (2d)
2
4
7, C3), 133.0 (d, JPC 10, ortho-Ph), 131.4 (d, JPC 3, para-Ph), 128.8
Dindenylphenylphosphine (0.547 g, 1.62 mmol) was dissolved in
dichloromethane (40 mL). Borane dimethylsulfide (0.81 mL, 2.0 mol
L
The solution was filtered through an alumina column (10 × 1.5 cm)
and the solvent evaporated under reduced pressure to afford diindenyl-
phenylphosphine borane (2d) (0.240 g, 42%) as a light-yellow powder.
δH (CDCl3) 7.8 (2 H, m, H4), 7.5 (6 H, m, H7, meta-Ph, ortho-Ph), 7.2
3
1
d, JPC 10, meta-Ph), 128.1 (d, JPC 59, ipso-Ph), 126.5 (s, C5), 125.6
s, C6), 123.9 (s, C7), 122.9 (s, C4), 40.2 (d, JPC 11, C1). δP{H} (CDCl3)
3
−1
, 1.62 mmol) was added and the reaction mixture stirred overnight.
0.77 (br).
Preparation of Diindenylphenylphosphine (2)
[7]
LensinkandGainsford obtainedanoilandreportedtheirNMRspectra
inC6D6.Wereporthereasynthesisthatproducesapowderandwereport
the NMR spectra in CDCl3 for consistency with the other compounds
reported here.
3
3
(5 H, m, H5, H6, para-Ph), 6.96 (2 H, dt, JPH 9.3, JHH 2.0, H2), 3.57
2
(4 H, s, H1), 1.3 (3 H, m, BH3). δC{H} (CDCl3) 148.05 (d, JPC 8, C2),
3
2
1
144.05 (d, JPC 8, C7a), 142.89 (d, JPC 12, C3a), 133.45 (d, JPC 59,

Oxide, Sulfide, Selenide, and Borane Derivatives of Indenylphosphines
1159
2
4
2
1
C3), 133.05 (d, JPC 10, ortho-Ph), 131.48 (d, JPC 2, para-Ph), 128.84
JPC 12, C3a), 132.3 (d, JPC 59, C3), 126.5 (s, C5), 125.5 (s, C6), 123.8
d, JPC 10, meta-Ph), 127.29 (d, 1JPC 60, ipso-Ph), 126.54 (s, C5),
25.59 (s, C6), 123.92 (s, C7), 122.87 (s, C4), 40.25 (d, JPC 11, C1).
3
(s, C7), 122.8 (s, C4), 40.2 (d, JPC 11, C1). δP{H} (CDCl3) −8.70 (br).
3
(
3
1
δP{H} (CDCl3) 1.21 (br).
Preparation of Pentacarbonyl(triindenylphosphine)-
Molybdenum(0) (3e)
Preparation of Triindenylphosphine (3)
Triindenylphosphine (0.251 g, 0.67 mmol) was dissolved in tetrahydro-
furan (25 mL) and hexacarbonylmolybdenum (0.176 g, 0.67 mmol)
added. This was stirred overnight before being heated to reflux for
Heuer et al. prepared triindenylphosphine from lithium indenide and
triphenylphosphite under reflux in diethyl ether and obtained a 37%
[4]
yield. We report here a higher-yielding synthesis.
1
.5 h. The solvent was removed under vacuum and the solid redissolved
To a solution of indene (3.3 g, 3.0 mmol) in diethyl ether (100 mL)
in diethylether. This was filtered through a column containing silica
to give pentacarbonyl(triindenylphosphine)molybdenum(0) (3e) (0.189
g, 42%) as a yellow powder upon removal of solvent in vacuo. (Found:
◦
n
at −78 C was added a solution of Bu Li (18.8 mL, 1.6 M, 3.0 mmol).
After warming to ambient temperature, the solution was stirred for 1 h
◦
and cooled again to −78 C. PCl3 (1.37 g, 1.0 mmol) was then added and
−1
C 61.80, H 3.82%. C32H21MoO5P requires C 62.76, H, 3.46%). ν/cm
the solution was then stirred for 2 h at ambient temperature before filter-
ing through an alumina column (10 × 1.5 cm).The solvent was removed
in vacuo and the residue washed with methanol to give triindenylphos-
(
7
KBr)2071s, 1987s, 1933vs, br, 1898ms, sh, 1713w, 1458mw, 1263m,
60 m, 719 mw, 583 mw, 419 w. δH (CDCl3) 7.57 (6 H, m, H4, H7), 7.26
2
(
2
(
(
δ
9 H, m, H2, H5, H6), 3.69 (6 H, s, H1). δC{H} (CDCl3) 209.9 (d, JPC
1
13
31
phine (3) (2.2 g, 60%) as a cream powder. H, C, and P NMR were
consistent with that reported by Heuer et al.
2
2
2, trans-CO), 205.9 (d, JPC 9, cis-CO), 145.4 (d, JPC 11, C2), 144.3
[
4]
3
2
1
d, JPC 7, C7a), 143.1 (d, JPC 11, C3a), 136.5 (d, JPC 37, C3), 125.9
3
s, C5), 125.3 (s, C6), 123.9 (s, C7), 122.9 (s, C4), 39.7 (d, JPC 10, C1).
+
+
Preparation of Triindenylphosphine Oxide (3a)
(CDCl ) −8.72. m/z (EI) 614 (4%, M ), 586 (10, [M–CO] ), 558
P{H}
3
+
+
+
(
[
82, [M–2 CO] ), 530 (8, [M–3 CO] ), 502 (5, [M–4 CO] ), 474 (73,
P(C9H6)3Mo] ), 472 (100, [P(C9H6)3Mo–2 H] ).
Triindenylphosphine (0.249 g, 0.66 mmol) was dissolved in toluene
+
+
(
25 mL) and an excess of aqueous hydrogen peroxide (1 mL, 50%
w/w) added. This was stirred overnight before the reaction mixture
was filtered and the solvent evaporated under vacuum. Recrystallization
Preparation of 1,3-Bis(diphenylphosphino)indene Diborane (4d)
,3-Bis(diphenylphosphino)indene (0.595 g, 1.23 mmol) was dissolved
in dichloromethane (50 mL). Borane dimethylsulfide (1.23 mL, 2.0 M,
.46 mmol) was added and the solution was then stirred overnight at
(
(
dichloromethane/petroleum ether) afforded triindenylphosphine oxide
1
+
•
3a) (0.198 g, 80%) as a light-brown solid. (Found: M 392.13439.
+
•
−1
C27H21OP requires M 392.13300). ν/cm (KBr) 2961 s, 1713 s,
2
1
6
458 s, 1381 ms, 1261 vs, 1236 s, 1022 vs, br, 959 s, 806 vs, 717 s,
ambient temperature. The solution was filtered through an alumina
column (10 × 1.5 cm) and the solvent removed in vacuo to give 1,3-
bis(diphenylphosphino)indene diborane (4d) (0.212 g, 34%) as a white
powder. δH (CDCl3) 7.6–7.0 (23 H, m), 6.88 (1 H, m), 6.57 (1 H, m,
4
46 s, 605 w, 498 s. δH (CDCl3) 7.74 (3 H, dd, JPH 3.5, 5.5, H4), 7.50
3
(
3 H, m, H7), 7.24 (6 H, m, H5, H6), 7.15 (3 H, d, JPH 10, H2), 3.59
2
3
(
6 H, s, H1). δC{H} (CDCl3) 147.4 (d, JPC 11, C2), 143.8 (d, JPC 10,
C7a), 133.0 (d, JPC 9, C3a), 128.8 (d, 1JPC 10, C3), 126.6 (s, C5),
2
2
H2), 4.68 (1 H, br d, JPH 18, H1), 1.3 (6 H, m, BH3). δC{H} (CDCl3)
3
1
25.6 (s, C6), 123.8 (s, C7), 122.7 (s, C4), 40.1 (d, JPC 14, C1). δP{H}
2
2
2
1
1
45.20 (dd, JPC 7, 2, C2), 133.48 (d, JPC 9, ortho-Ph), 133.07 (d, JPC
+
+
(
CDCl3) 10.03. m/z (EI) 392 (13%, M ), 277 (31, [M–C9H7] ), 201
2
2
0, ortho-Ph), 132.87 (d, JPC 10, ortho-Ph), 132.34 (d, JPC 9, ortho-
Ph), 132.22 (d, JPC 3, para-Ph), 131.62 (d, JPC 3, para-Ph), 131.58
d, JPC 3, para-Ph), 131.42 (d, JPC 3, para-Ph), 128.90 (d, JPC 10,
PC PC
meta-Ph), 128.83 (d, J 10, meta-Ph), 128.83 (d, J 10, meta-Ph),
+
+
(
20, C12H10OP ), 115 (100, C9H ).
4
4
7
4
4
3
(
3
3
Preparation of Triindenylphosphine Sulfide (3b)
3
1
28.72 (d, JPC 10, meta-Ph), 127.81 (s, C5), 125.98 (s, C6), 124.44 (s,
An excess of elemental sulfur (0.100 g, 1.37 mmol) was suspended in a
freshly prepared solution of triindenylphosphine (0.258 g, 0.69 mmol) in
diethyl ether (25 mL) and stirred overnight at ambient temperature. The
reaction mixture was filtered through a column containing silica and the
solvent evaporated under vacuum. Recrystallization was carried out first
using dichloromethane and petroleum ether. A second recrystallization
3
1
C7), 123.60 (s, C4), 49.61 (dd, JPC 11, JPC 26, C1). No peaks could
be unambiguously assigned to quaternary carbon atoms. δP{H} (CDCl3)
2
5.67 (br), 11.41 (br).
Preparation of rac-Bis(1-(diphenylphosphino)indenyl)iron(II)
Diborane (5d)
(
hot ethanol) afforded triindenylphosphine sulfide (3b) (0.178 g, 64%)
+
•
+•
as a yellow powder. (Found: M 408.10979. C27H21PS requires M
4
To a solution of rac-bis(1-(diphenylphosphino)indenyl)iron(ii) (0.51 g,
−1
08.11016). ν/cm (KBr) 3317 s, br, 2963 s, 1458 s, 1381 s, 1263
0
.811 mmol) in tetrahydrofuran (30 mL) was added a solution of borane
s, 1236 m, 1096 vs, 1020 vs, 800 vs, 760 vs, 679 s, 640 ms, 613 m.
dimethylsulfide complex (1.1 mL, 2 M, 2.2 mmol).The reaction mixture
was stirred at ambient temperature for 12 h. The mixture was filtered
through Celite and the solvent removed in vacuo to leave a brown
residue. Chromatography of the residue on silica gel afforded rac-bis(1-
δH (CDCl3) 7.81 (3 H, m, H4), 7.50 (3 H, m, H7), 7.24 (6 H, m, H5,
3
H6), 7.17 (3 H, d, JPH 11, H2), 3.58 (6 H, s, H1). δC{H} (CDCl3) 147.0
2
3
2
(
(
d, JPC 10, C2), 144.1 (d, JPC 10, C7a), 142.0 (d, JPC 12, C3a), 136.2
1
d, JPC 90, C3), 126.5 (s, C5), 125.6 (s, C6), 123.9 (s, C7), 123.0 (s,
(
diphenylphosphino)indenyl)iron(II) diborane (5d) (0.46 g, 83%) as a
3
C4), 39.8 (d, JPC 15, C1). δP{H} (CDCl3) 9.60 (s). m/z (EI) 408 (10%,
brown powder. (Found: C 72.06, H 5.62%. C42H38B2FeP2 requires
C 73.95, H 5.62%). δH (CDCl3) 7.6–6.4 (28 H, m, H4–H7 and Ph),
+
+
+
+
M ), 259 (14, [M–C9H9S] ), 230 (21, C18H ), 146 (35, C9H6S ),
1
4
+
3
3
1
15 (100, C9H ).
HH HH
5.81 (2 H, d, J 2.4, H3), 3.42 (2 H, t, J 2.4, H2), 1.65 (6 H, m,
7
2
2
BH3). δC{H} (CDCl3) 135.4 (d, JPC 21, o-Ph), 132.4 (d, JPC 20, o-Ph),
4
1
4
Preparation of Triindenylphosphine Borane (3d)
131.2 (d, JPC 2, p-Ph), 131.0 (d, JPC 58, ipso-Ph), 130.8 (d, JPC 3,
1
3
p-Ph), 129.9 (d, JPC 60, ipso-Ph), 128.5 (d, JPC 6, m-Ph), 128.4 (d,
JPC 6, m-Ph), 125.7 (s, C5), 124.0 (s, C6), 123.3 (s, C7), 123.2 (s, C4),
1.0 (d, JPC 7, C7a), 89.3 (d, JPC 13, C3a), 73.5 (d, JPC 4, C2), 68.3
d, JPC 5, C3), 62.0 (d, JPC 64, C1). δP{H} (CDCl3) 16.53 (br).
Triindenylphosphine (0.285 g, 0.76 mmol) was dissolved in dichloro-
3
−
1
methane (40 mL). Borane dimethylsulfide (0.45 mL, 2 mol L
,
3
2
2
9
(
0
.91 mmol) was added and the reaction mixture stirred overnight. The
3
1
solvent was evaporated under reduced pressure and the product recrys-
tallized (dichloromethane/petroleum ether). A further recrystallization
Crystal Structure, Data Collections, Solutions, and Refinements
(
hot ethanol) afforded triindenylphosphine borane (3d) (0.210 g, 71%)
−
1
as a light-yellow powder. ν/cm (KBr) 2399 s, 2357 ms, 1711 ms,
458 s, 1375 ms, 1065 s, 1020 ms, 914 mw, 764 s, 716 s, 499 vs.
For each compound, a crystal was attached to a thin glass fibre and
mounted on a Siemens P4 SMART diffractometer with a Siemens CCD
1
δH (CDCl3) 7.64 (3 H, m, H4), 7.49 (3 H, m, H7), 7.22 (6 H, m, H5,
area detector. Empirical absorption corrections were determined with
3
[28]
H6), 7.13 (3 H, dm, JPH 9, H2), 3.58 (6 H, s, H1), 1.1 (3 H, m, BH3).
SADABS and applied to the data.
Data processing was undertaken
2
3
[28]
δC{H} (CDCl3) 147.8 (d, JPC 7, C2), 144.0 (d, JPC 8, C7a), 142.9 (d,
with SAINT
and the structures were solved by direct methods and

1
160
O. J. Curnow et al.
2
refined by full-matrix least-squares methods on F using the SHELXTL
program library.
[11] K. H. Doetz, I. Pruskil, U. Schubert, K. Ackermann, Chem.
Ber. 1983, 116, 2337.
[29]
Hydrogen atoms were placed in their calculated
positions and refined isotropically. Non-hydrogen atoms were refined
anisotropically.
[12] O. J. Curnow, G. M. Fern, Organometallics 2002, 21, 2827.
[13] I. E. Nifant’ev, P. V. Ivchenko, Organometallics 1997, 16, 713.
[14] A. Vogel, T. Priermeier, W. A. Herrmann, J. Organomet. Chem.
1997, 527, 297.
[15] J. L. Huhmann, J. Y. Corey, N. P. Rath, Organometallics 1996,
15, 4063.
[16] S. C. Sutton, M. H. Nantz, S. R. Parkin, Organometallics 1993,
12, 2248.
[17] Y. Chen, M. D. Rausch, J. C. W. Chien, Organometallics 1993,
12, 4607.
[18] R. L. Halterman, Chem. Rev. 1992, 92, 965, and references
therein.
[19] M. Concepcion, P. G. Jones, A. Laguna, C. Sarroca, J. Chem.
Soc. Dalton Trans. 1995, 3563, and references therein.
[20] R. Broussier, S. Ninoreille, C. Legrand, B. Gautheron,
J. Organomet. Chem. 1997, 532, 55.
Diindenylphenylphosphine Selenide (2c). C24H19PSe, M 417.32,
monoclinic, space group P21/n,
c 19.3353(9) Å, β 101.025(1) , V 1966.04(16) Å , T 160(2) K,
a 14.4260(7), b 7.1810(3),
◦
3
−
3
Dcalc 1.410 g cm , Z 4, crystal size 0.50 × 0.36 × 0.10 mm, λ(MoKα)
−
1
0
0
.71073 Å, µ(MoKα) 1.995 mm , F(000) 848, T(SADABS)min,max
◦
.435, 0.825, 2θmax 48 , hkl range −16 ≤ h ≤ 16, −8 ≤ k ≤ 7,
−
22 ≤ l ≤ 21, N 13 348, Nind 3072 (Rint 0.040), no. of parameters 235,
−
3
R (I > 2σ(I)) 0.063, Rw 0.167, ρmax,min 1.16, −0.77 e Å
.
Triindenylphosphine Sulfide (3b). C27H21PS, M 408.47, tri-
¯
clinic, space group P1, a 8.9640(18), b 10.745(2), c 12.560(3) Å,
◦
3
α 99.41(3), β 98.26(3), γ 113.90(3) , V 1061.2(4) Å , T 293(2) K,
−3
Dcalc 1.278 g cm , Z 2, crystal size 0.35 × 0.26 × 0.15 mm, λ(MoKα)
−
1
0
0
.71073 Å, µ(MoKα) 0.239 mm , F(000) 428, T(SADABS)min,max
◦
.921, 0.965, 2θmax 53.6 , hkl range −9 ≤ h ≤ 9, −13 ≤ k ≤ 13,
−
15 ≤ l ≤ 15, N 5417, Nind 2806 (Rint 0.099), no. of parameters 262,
[21] S. Ninoreille, R. Broussier, R. Amardeil, M. M. Kubicki,
B. Gautheron, Bull. Soc. Chim. Fr. 1995, 132, 128.
−
3
R (I > 2σ(I)) 0.059, Rw 0.115, ρmax,min 0.28, −0.26 e Å
.
[
22] V. I. Bakhmutov, M. Visseaux, D. Baudry, A. Dormond,
P. Richard, Inorg. Chem. 1996, 35, 7316.
Accessory Materials
[
23] S. Berger, S. Braun, H.-O. Kalinowski, in NMR Spectroscopy
of the Non-metallic Elements 1996, p. 806 (John Wiley:
Chichester).
Crystallographic data for this paper has been deposited with
the Cambridge Crystallographic Data Centre (nos. 199 507
for (2c) and CCDC 199 506 for (3b)).
[
24] S. Berger, S. Braun, H.-O. Kalinowski, NMR Spectroscopy of
the Non-metallic Elements 1996 (John Wiley: Chichester).
25] S. O. Grim, W. McFarlane, Nature 1965, 208, 995.
26] A. Schmidpeter, H. Brecht, Z. Naturforsch. 1968, 23B, 1529.
[
[
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