Rhodium and iridium complexes bearing an alkyloxazoline-substituted indenyl ligand (Indox ligand) and their stereoselective construction of metal-centered chirality

Article abstract of DOI:10.1016/j.ica.2004.05.031

The Indox ligands, [{(S)-(ⁱPr)Indox}_n]H (1) [n=2 (a), 3 (b)] and [{(H)Indox}_n=3]H (2), in which an indenyl group and an oxazoline ring are connected by an ethylene or propylene spacer, have been prepared. Reaction of [Ir(coe)₂Cl]₂ or [RhCl(C ₂H₄)₂]₂ with the potassium salt of 1 afforded η⁵-[{(S)-(ⁱPr)Indox}_n]Ir(coe) ₂ (3) or η⁵-[{(S)-(ⁱPr)Indox} _n]Rh(C₂H₄)₂ (6) as a 1:1 mixture of two diastereomers. The oxazoline ring in 3 and 6 did not coordinate to the metal center. When the complexes 3 or 6 reacted with iodine in diethyl ether, oxidative addition proceeded and the oxazoline ring coordinated to the metal center to give diiodoiridium(III) or rhodium(III) complexes, η⁵:η¹-[{(S)-(ⁱPr)Indox} _n]M(I)₂ [M=Ir (4), Rh (7)]. The corresponding diiodoiridium(III) complex bearing the Indox ligand 2, η⁵: η¹-[{(H)Indox}_n=2]Ir(I)₂ (5), was also prepared by a similar method. Reaction of 4 or 7 with PPh₃ in THF afforded diiodo-phosphine complexes, η⁵-[{(S)-( ⁱPr)Indox}_n]M(PPh₃)(I)₂ [M=Ir (8), Rh (9)] as a 1:1 mixture of two diastereomers in which the oxazoline ring dissociated from the metal center. The related reaction of 8 or 9 with more than 2 equiv. of AgOTf afforded the cationic complexes, [η⁵: η¹-[{(S)-(ⁱPr)Indox}_n]M(PPh ₃)(OTf)]OTf [M=Ir (10), Rh (11)], having a stereogenic center at the metal center as a mixture of only two diastereomers. From ¹H and ³¹P NMR analyses, each diastereomer of 8 or 9 afforded only a single isomer of 10 or 11. The corresponding iridium(III) complex bearing the Indox ligand 2, [η⁵:η¹-[{(H)Indox}_n=3] Ir(PPh₃)(OTf)]OTf (12) was also prepared. The coordinated triflate ligand of 12 was slowly replaced by water in CDCl₃ to afford the dicationic aquo complex, (S*_pl,R*_Ir)- [η⁵:η¹-[{(H)Indox}_n=3]Ir(PPh ₃)(H₂O)](OTf)₂ (13). The monocationic complex, [η⁵:η¹-[{(S)-(ⁱPr)Indox} _n=2]Ir(PPh₃)(I)]OTf (14a), having metal-centered chirality, was observed as a mixture of only two diastereomers in the reaction of 10a (a mixture of two diastereomers) with 1 equiv. of AgOTf. These observations indicated that the ligand exchange reaction of 8 or 9 with AgOTf contained the following three steps: (i) abstraction of one of the two prochiral iododes by AgOTf, (ii) recoordination of the oxazoline ring, and (iii) exchange of the remaining iodide for the triflate by AgOTf. The stereochemistry around the metal center was determined at the second step. All complexes have been characterized by usual spectroscopic methods as well as elemental analyses, and 4 and 13 have been characterized by X-ray analyses.

Full text of DOI:10.1016/j.ica.2004.05.031

Inorganica Chimica Acta 357 (2004) 2965–2979
www.elsevier.com/locate/ica
Rhodium and iridium complexes bearing an
alkyloxazoline-substituted indenyl ligand (Indox ligand) and
their stereoselective construction of metal-centered chirality
a,
a
a
a
Yasutaka Kataoka *, Koichi Shimada , Takahiro Goi , Tsuneaki Yamagata ,
a
Kazushi Mashima , Kazuhide Tani
b,
*
a
Department of Chemistry, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama,Toyonaka, Osaka 560-8531, Japan
b
Higashiosaka University, Higashiosaka, Osaka 577-8567, Japan
Received 9 January 2004; accepted 15 May 2004
Available online
Abstract
The Indox ligands, [{ðSÞ-(iPr)Indox}n]H (1) [n ¼ 2 (a), 3 (b)] and [{(H)Indox}n¼3]H (2), in which an indenyl group and an ox-
azoline ring are connected by an ethylene or propylene spacer, have been prepared. Reaction of [Ir(coe)2Cl]2 or [RhCl(C2H4)2]2 with
the potassium salt of 1 afforded g5-[{ðSÞ-(iPr)Indox}n]Ir(coe)2 (3) or g5-[{ðSÞ-(iPr)Indox}n]Rh(C2H4)2 (6) as a 1:1 mixture of two
diastereomers. The oxazoline ring in 3 and 6 did not coordinate to the metal center. When the complexes 3 or 6 reacted with iodine
in diethyl ether, oxidative addition proceeded and the oxazoline ring coordinated to the metal center to give diiodoiridium(III) or
rhodium(III) complexes, g5:g1-[{ðSÞ-(iPr)Indox}n]M(I)2 [M ¼ Ir (4), Rh (7)]. The corresponding diiodoiridium(III) complex bearing
the Indox ligand 2, g5:g1-[{(H)Indox}n¼2]Ir(I)2 (5), was also prepared by a similar method. Reaction of 4 or 7 with PPh3 in THF
afforded diiodo-phosphine complexes, g5-[{ðSÞ-(iPr)Indox}n]M(PPh3)(I)2 [M ¼ Ir (8), Rh (9)] as a 1:1 mixture of two diastereomers
in which the oxazoline ring dissociated from the metal center. The related reaction of 8 or 9 with more than 2 equiv. of AgOTf
afforded the cationic complexes, [g5:g1-[{ðSÞ-(iPr)Indox}n]M(PPh3)(OTf)]OTf [M ¼ Ir (10), Rh (11)], having a stereogenic center at
the metal center as a mixture of only two diastereomers. From 1H and 31P NMR analyses, each diastereomer of 8 or 9 afforded only
a
single isomer of 10 or 11. The corresponding iridium(III) complex bearing the Indox ligand 2, [g5:g1-[{(H)In-
dox}n¼3]Ir(PPh3)(OTf)]OTf (12) was also prepared. The coordinated triflate ligand of 12 was slowly replaced by water in CDCl3 to
afford the dicationic aquo complex, ðSpꢀl; RꢀIrÞ-[g5:g1-[{(H)Indox}n¼3]Ir(PPh3)(H2O)](OTf)2 (13). The monocationic complex, [g5:g1-
[{ðSÞ-(iPr)Indox}n¼2]Ir(PPh3)(I)]OTf (14a), having metal-centered chirality, was observed as a mixture of only two diastereomers in
the reaction of 10a (a mixture of two diastereomers) with 1 equiv. of AgOTf. These observations indicated that the ligand exchange
reaction of 8 or 9 with AgOTf contained the following three steps: (i) abstraction of one of the two prochiral iododes by AgOTf, (ii)
recoordination of the oxazoline ring, and (iii) exchange of the remaining iodide for the triflate by AgOTf. The stereochemistry
around the metal center was determined at the second step. All complexes have been characterized by usual spectroscopic methods
as well as elemental analyses, and 4 and 13 have been characterized by X-ray analyses.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Indox ligand; Oxazoline ring; Metal-centered chirality; Planar chirality; Ligand exchange reaction; Hemilabile
1. Introduction
amide, sulfide and alcohol are connected by an appro-
priate spacer, have received much attention as hetero-
functional ligands having the combined characters of
their components, which could often induce some un-
expected reactivities [1]. So far, we have concentrated on
the chemistry of the linked cyclopentadienyl (or indenyl)
and phosphine ligand (the Cp0–P ligand) and disclosed
the unique characters of their rhodium, iridium and
Hybrid ligands, in which both a cyclopentadienyl
derivative and a donor-ligand such as phosphine, amine,
* Corresponding authors. Tel.: +81-6-6850-6246; fax: +81-6-6850-
6249.
E-mail address: kataoka@chem.es.osaka-u.ac.jp (Y. Kataoka).
0020-1693/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2004.05.031

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Y. Kataoka et al. / Inorganica Chimica Acta 357 (2004) 2965–2979
ruthenium complexes [2]. One significant character was
the stereoselective construction of metal-centered chi-
rality controlled by the planar chirality arising from the
complexation of the Cp0–P ligand having an indenyl
group [2c,2d,2e]. On the other hand, a wide variety of
metal complexes having the Cp0–N ligand, in which an
amino group was linked to a cyclopentadienyl deriva-
tive, have also been prepared and their reactivities were
examined [1a,1b,1c]. Early transition metals and lan-
thanide complexes bearing the Cp0–N ligand are ex-
pected to be a post-metallocen catalyst [3]. Although
late transition metals bearing the Cp0–N ligand have
also provided many interesting properties including
hemilability of the N-donor part, stabilization of un-
stable species, creation of bimetallic complexes and so
on, several unexplored but fascinating fields still remain
[4–10]. One is the utilization of an oxazoline ring as an
N-donor ligand in the Cp0–N ligand. An optically active
oxazoline ring is easily prepared from an amino alcohol
and the complexes bearing the oxazoline-based chiral
ligands are known as an effective asymmetric catalyst.
The Cp0–N ligand having an optically active oxazoline
ring could be effective in catalytic asymmetric reactions.
Another is the preparation of the complexes having a
stereogenic center on the metal by using the Cp0–N li-
gand. A three-legged piano stool complex, Cp0ML1L2L3
(Cp0 ¼ cyclopentadienyl derivative, M ¼ metal and Ln ¼
ligand), has a stereogenic center on the metal if all li-
gands are different, but optically active complexes like
that are usually troublesome to be prepared due to
configurational instability of the chirality on the metal
center. We already showed that a stable stereogenic
center on the metal could be constructed by using the
Cp0–P ligand. Although coordination of the N-donor is
weaker than that of the P-donor, the Cp0–N ligand has
possibility to create stable metal-centered chirality.
Herein, we report the preparation of a new series of
the Cp0–N ligand, the Indox ligand, in which an opti-
cally active oxazoline ring as an N-donor and an indenyl
group as a cyclopentadienyl derivative are connected by
an alkylene spacer, and the synthesis and characteriza-
tion of their iridium and rhodium complexes. Studies on
the construction of metal-centered chirality by the ster-
eoselective ligand exchange reaction of their iridium and
rhodium complexes having two prochiral iodide ligands
are also presented.
Scheme 1.
two steps as shown in Scheme 1. Treatment of the lith-
n
ium salt of indene, prepared from indene and BuLi in
THF at 0 °C, with 3-bromopropanenitrile or 4-bromo-
butanenitrile afforded 3-(3-indenyl)propanenitrile or 4-
(3-indenyl)butanenitrile, respectively. Conversion of the
nitrile group into an oxazoline ring by the ZnCl2-cata-
lyzed annulation with ðSÞ-valinol or 2-aminoethanol
gave the Indox ligands 1 or 2 in moderate to good yields
[11]. This methodology can supply several Indox ligands
having a different alkylene spacer, but unfortunately the
Indox ligand having a methylene spacer could not be
prepared because the reaction of bromoacetonitrile with
the lithium salt of indene gave a complex mixture.
2.2. Synthesis and characterization of diiodo complexes
bearing the Indox ligand
The Indox ligands 1 were treated with KH in THF at
80 °C for 1 h and the resulting brown suspension was
added to a THF suspension of [Ir(coe)2Cl]2 at 0 °C. The
reaction mixture was warmed to room temperature
overnight and resulted in a dark red solution. After the
solvent was removed in vacuo, the iridium complexes,
g5-[{ðSÞ-(iPr)Indox}n]Ir(coe)2 (3), were isolated by ex-
traction with hexanes from the resulting residue (Eq.
(1)). Purification of 3 by recrystallization failed due to
the too rich solubility of 3 to various solvents, but the
purity was satisfactory for the identification of 3 by
spectroscopic methods and the utilization for the fol-
lowing reactions. Abstraction of the proton in the in-
denyl group by KH was indispensable for the
preparation of the iridium complexes. A similar reaction
using nBuLi or tBuLi instead of KH, which were usually
used for the preparation of the rhodium or iridium
complexes having the indenyl group, afforded many
undefined impurities along with a small amount of 3
[12]. The molecular ion peak at m/e 667 (3a) and 682 (3b)
in the mass spectra supported the proposed structure of
3. The IR spectra showed the C@N stretching vibration
2. Results and discussion
2.1. Synthesis of the Indox ligand
The Indox ligands, [{ðSÞ-(iPr)Indox}n]H (1) [n ¼ 2
(a), 3 (b)] and [{(H)Indox}n¼3]H (2), in which an indenyl
group and an oxazoline ring are connected by an eth-
ylene or propylene spacer, were prepared from indene by

Y. Kataoka et al. / Inorganica Chimica Acta 357 (2004) 2965–2979
2967
at 1669 cmꢁ1 (3a and 3b), which was hardly shifted from
that of the free ligand (1a, 1672 cmꢁ1; 1b, 1670 cmꢁ1),
indicating that the oxazoline ring did not coordinate to
protons in the indenyl group appeared as two sets of two
doublets with the same integral intensities (4a, d 5.83,
5.93 and 5.86, 5.06; 4b, d 5.77, 6.17 and 5.82, 6.21), in-
dicating that both 4a and 4b were also a 1:1 mixture of
two diastereomers derived from the planar chirality and
the stereogenic center in the oxazoline ring. It was rea-
sonable that the ratio of the two diastereomers in 4 was
the same as that of 3 because the oxidative iodination
proceeded with no influence on the stereochemistry of
the two chiralities. The ratio of the two diastereomers in
3b, which was not confirmed by the 1H NMR analysis of
3b, could be determined to be 1:1 from these observa-
tions. Although we tried to isolate the diastereoisomer-
ically pure form of 4 by repeated recrystallization,
unfortunately our attempts have not been succeeded yet.
1
the iridium center. The H NMR analysis of the crude
product showed that 3a was obtained as a 1:1 mixture of
two diastereomers due to combination of the arising
planar chirality and the stereogenic center of the oxaz-
oline ring. The terminal proton in the isopropyl group of
3a was observed as two sets of two doublet signals with
the same integral intensities (d 0.81, 0.93 and 0.84, 0.89).
Although the ratio of the diastereomers in 3b could not
be determined directly from the 1H NMR spectrum
because the signals were not unambiguously distin-
guished between the diastereomers, we estimated that 3b
also formed as a 1:1 mixture of the diastereomers from
the following experiments (vide infra). In the complex-
ation of the Indox ligand with the iridium metal, the
stereogenic center in the oxazoline ring was ineffective
for the induction of the arising planar chirality on the
indenyl ring. Whitby and co-workers [13] reported that
the coordination of the phosphino group to the metal
center was essential for a high level of induction of
planar chirality in the complexation of the Cp0–P type
ligand. The stereogenic center of the oxazoline ring in
the Indox ligand would locate remote to the metal center
where the nucleophilic attack of the potassium salt of
the indenyl group occurred. One reason is the weaker
coordination ability of the oxazoline ring as an N-donor
to the iridium(I) metal.
ð2Þ
Single crystals of 4b suitable for X-ray analysis were
directly obtained from the reaction mixture under dilute
conditions. An ORTEP drawing is given in Fig. 1, rele-
vant crystal and data parameters are presented in Table 1,
and selected bond lengths and angles are given in Table 2.
The unit cell contained two diastereomers, ðRplÞ-4b which
was the complex containing Ir1 and ðSplÞ-4b which was
the complex containing Ir2. These crystals were in the
monoclinic space group P21 with four molecules in the
unit cell (two independent molecules are in the asym-
metric unit). The dihedral angle between the least-square
plane of the indenyl ring and the least-square plane of the
oxazoline ring in ðRplÞ-4b was 30.24(47)°, while that in
ðSplÞ-4b was 65.56(27)°. In order to avoid the steric re-
pulsion between the isopropyl group in the oxazoline ring
and the phenyl ring in the indenyl group, the isopropyl
group in ðSplÞ-4b pointed away from the indenyl ring and
the oxazoline ring coordinated to the iridium center with
a slight leaning to the vertical direction compared to that
in ðRplÞ-4b. The steric repulsion was also reflected in the
N–Ir–Cpn angles [Cpn (n ¼ 1 or 2) is the gravimetric
center of the cyclopentadienyl part of the indenyl group]:
The N2–Ir2–Cp2 bond angle (130.51°) in ðSplÞ-4b is larger
than the N1–Ir1–Cp1 bond angle (124.92°). The distor-
tion of the indenyl ring towards g3-coordination was not
observed clearly compared to that in the rhodium and
iridium complexes having the Cp0–P type ligand, but it is
undeniable. For example, the bond lengths of Ir1–C4
ð1Þ
Reaction of 3 with 1 equiv. of elemental iodine in
diethyl ether at room temperature according to the
method of Jutzi afforded the diiodoiridium(III) com-
plexes, g5:g1-[{ðSÞ-(iPr)Indox}n]Ir(I)2 (4), in excellent
yields (Eq. (2)) [7b]. The structure of 4 was confirmed by
elemental analyses and spectroscopic methods. The IR
spectra showed the C@N stretching vibration at 1632
cmꢁ1 (4a and 4b), which was shifted to a lower wave
number by ca. 40 cmꢁ1 compared to that of the free li-
gand, indicating that the Indox ligand coordinated to
the iridium center in an g5- and g1-coordination man-
ner. In the FAB mass spectra, the molecular ion peak at
ꢀ
ꢀ
(2.253(10) A) or Ir1–C5 (2.234(9) A) in ðRplÞ-4b and Ir2–
ꢀ
ꢀ
C22 (2.246(9) A) or Ir2–C23 (2.292(8) A) in ðSplÞ-4b were
a little longer than those of other bonds in the ranges
ꢀ
2.135–2.182 A. The two Ir–I bond lengths are different:
1
m/e 701 (4a) and 716 (4b) was observed. The H NMR
spectra showed that the signals of the cyclopentadienyl
ꢀ
The bond lengths of Ir1–I1 (2.7248(8) A) and Ir2–I4

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Y. Kataoka et al. / Inorganica Chimica Acta 357 (2004) 2965–2979
action of g5-[{ðSÞ-(iPr)Indox}n]Rh(C2H4)2 (6), obtained
from the potassium salt of 1 with [RhCl(C2H4)2]2 in
THF, with iodine in diethyl ether. The structure of these
complexes was characterized by usual spectroscopic
methods as well as elemental analyses, though an ana-
lytically pure form of 6 was not obtained due to its too
rich solubility to various solvents. The 1H NMR spectra
showed that 7 was also an almost 1:1 mixture of two
diastereomers, indicating that the stereogenic center in
the oxazoline ring did not induce the planar chirality at
all for the complexation with the rhodium in the same
way as the iridium complexes.
2.3. Synthesis and characterization of diiodo-phosphine
complexes bearing the g1-coordinated Indox ligand
When the diiodoiridium(III) complexes 4 (1:1 mixture
of two diastereomers) were treated with 1 equiv. of PPh3
in THF at room temperature for 3 h, the oxazoline ring
dissociated from the iridium center to afford the diiodo-
phosphine complexes, g5-[{ðSÞ-(iPr)Indox}n]Ir(PPh3)(I)2
(8) as a brown powder (Eq. (3)). In an analogous way,
reaction of the rhodium(III) complexes 7 with 1 equiv. of
PPh3 in THF at room temperature for 24 h gave similar
rhodium complexes, g5-[{ðSÞ-(iPr)Indox}n]-Rh(PPh3)-
(I)2 (9) as a brown powder (Eq. (3)). The structure of 8
and 9 was fully characterized by elemental analyses as
well as spectral data. Dissociation of the oxazoline ring
was confirmed by the IR spectra for the C@N stretching
Fig. 1. ORTEP drawing of two diastereomers, ðRplÞ-4b and ðSplÞ-4b, in
the asymmetric unit. Thermal ellipsoids are shown at the 50% proba-
bility level.
ꢀ
(2.7083(7) A) are similar to those of the two Ir–I bonds in
the diiodoiridium complexes having the Cp0–N type li-
vibration (8a, 1669 cmꢁ1; 8b, 1668 cmꢁ1; 9a, 1669 cmꢁ1
;
ꢀ
gand prepared by Jutzi [7b], but the Ir1–I2 (2.6562(7) A)
9b, 1667 cmꢁ1), which were hardly shifted from that of
the free ligand. The N-donor of the alkylamine-substi-
tuted cyclopentadienyl ligand in rhodium and iridium
complexes easily dissociated from the central metals in
the reaction with a phosphine, as reported by Jutzi [7b].
The 31P NMR spectra displayed two singlet signals with
the same integral intensities for 8 (8a, d 1.57, 1.60; 8b, d
1.58, 1.60) and two doublet signals (JP–Rh ¼ 155 Hz) for
9 (9a, d 48.1, 48.2; 9b, d 48.3, 48.4), respectively, indi-
cating that both 8 and 9 were also a 1:1 mixture of two
diastereomers. Repeated recrystallization from the mix-
tures did not afford the diastereoisomerically pure form,
but the diastereomer mixtures containing a little excess
amount of one diastereomer were obtained (8a, 55:45;
8b, 51:49; 9a, 57:43; 9b, 51:49).
ꢀ
and Ir2–I3 (2.6689(7) A) bonds are a little but clearly
shorter.
Reaction of the potassium salt of 2 with [Ir(coe)2Cl]2
in THF, followed by oxidation of iodine in diethyl ether
afforded the diiodoiridium(III) complex, g5:g1-
[{(H)Indox}n¼3]Ir(I)2 (5) as a brown powder in 67%
isolated yield. The IR spectrum at 1633 cmꢁ1 for the
C@N stretching vibration and mass spectrum at m/e 673
as a molecular ion peak suggested the formation of 5.
Since 5 was a 1:1 mixture of enantiomers based on the
planar chirality on the indenyl ring, the 1H NMR
spectrum showed the two protons of the cyclopenta-
dienyl part as one set of two doublets at d 5.91 and 6.04.
Similarly, the diiodorhodium(III) complexes, g5:g1-
[{ðSÞ-(iPr)Indox}n]Rh(I)2 (7) were prepared by the re-

Y. Kataoka et al. / Inorganica Chimica Acta 357 (2004) 2965–2979
2969
Table 1
Crystal data and structure refinement details for 4 and 13
4
13
Empirical formula
Formula weight
Temperature (K)
C18H22I2IrNO
714.34
296(2)
C36H34Cl3F6IrNO8PS2
1116.28
173(1)
ꢀ
Wavelength (A)
0.71069
monoclinic
P21 (#4)
0.71069
triclinic
Crystal system
Space group
Unit cell dimensions
ꢁ
P1 (#2)
ꢀ
a (A)
15.7847(9)
9.8925(6)
13.2358(7)
13.3151(2)
ꢀ
b (A)
ꢀ
c (A)
13.5100(8)
90
12.5460(3)
114.7063(6)
a (°)
b (°)
c (°)
110.0778(14)
90
1981.4(2)
94.932(2)
87.730(3)
2001.22(12)
3
ꢀ
Volume (A )
Z
4
2.395
2
1.853
Dcalc (Mg/m3)
Absorption coefficient (mmꢁ1
F ð000Þ
)
9.858
1312
3.761
1100
Crystal size (mm)
0.35 ꢂ 0.22 ꢂ 0.22
3.03–32.50
0.20 ꢂ 0.14 ꢂ 0.13
2.52–27.50
h Range for data collection (°)
Limiting indices
ꢁ235h523, ꢁ145k 514, ꢁ205l520
37 292
ꢁ175h517, ꢁ175k 517, ꢁ165l516
26 546
Reflections collected
Unique reflections
13 896 ½Rint ¼ 0:0841ꢃ
0.347875
0.156259
9056 ½Rint ¼ 0:1022ꢃ
0.728061
0.602144
Maximum transmission
Minimum transmission
Goodness-of-fit on F 2
Final R indices ½I > 2rðIÞꢃ
R indices [All data]
0.980
1.026
R1 ¼ 0:0516, wR2 ¼ 0:1164
R1 ¼ 0:0720, wR2 ¼ 0:1243
3.04 and )2.001
R1 ¼ 0:0659, wR2 ¼ 0:1430
R1 ¼ 0:0878, wR2 ¼ 0:1565
4.116 and )1.719
3
ꢀ
Largest difference peak and hole (e/A )
Table 2
ꢀ
Selected bond lengths (A) and bond angles (°) for ðRplÞ-4b and ðSplÞ-4b
(Rpl)-4b
Bond lengths
Ir1–C1
Ir1–C2
Ir1–C3
Ir1–C4
Ir1–C5
Ir1–I1
Ir1–I2
Ir1–N1
2.166(11)
2.135(9)
2.162(10)
2.253(10)
2.234(9)
2.7248(8)
2.6562(7)
2.112(8)
Bond angles
I1–Ir1–Cp1
I2–Ir1–Cp1
N1–Ir1–Cp1
120.95
127.32
124.92
ð3Þ
2.4. Construction of metal-centered chirality
(Spl)-4b
Bond lengths
Ir2–C19
Ir2–C20
Ir2–C21
Ir2–C22
Ir2–C23
Ir2–I3
2.182(9)
2.146(9)
2.137(9)
2.246(9)
2.292(8)
2.6689(7)
2.7083(7)
2.140(8)
Recoordination of the dissociated-oxazoline ring in 8
and 9 occurred by the ligand exchange reaction of two
prochiral iodide ligands to give the cationic complex
having a stereogenic center at the metal. For example,
reaction of 8a [ðSplÞ-8a:ðRplÞ-8a ¼ 55:45 or vice versa]
with more than 2 equiv. of AgOTf in dichloromethane at
room temperature for 3 h afforded the cationic iridium
Ir2–I4
Ir2–N2
complex,
[g5:g1-[{ðSÞ-(iPr)Indox}n¼2]Ir(PPh3)(OTf)]-
Bond angles
I3–Ir2–Cp2
I4–Ir2–Cp2
N2–Ir2–Cp2
125.66
120.27
130.51
OTf (10a), quantitatively as a yellow-brown powder
(Scheme 2). The structure of 10a was fully characterized
by elemental analysis as well as spectral data. The IR

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Y. Kataoka et al. / Inorganica Chimica Acta 357 (2004) 2965–2979
analysis supported the structure of 12. The 31P NMR
spectrum of the reaction mixture before purification
with only one singlet signal at d 10.6 indicated that 12
was a diastereoisomerically pure complex. The stereo-
chemistry of the arising stereogenic center at the iridium
was completely controlled by the Indox ligand regard-
less of having a chiral substituent or not in the oxazoline
ring. That is, the planar chirality on the indenyl ring
plays a determinant role in the induction of the stereo-
genic center on the metal.
ð4Þ
Yellow single crystals suitable for X-ray analysis were
obtained from a CDCl3 solution of 12 in the NMR tube
at room temperature for 4 days. An ORTEP drawing
described in Fig. 2 showed that the crystals were a di-
cationic aquo complex, [g5:g1-[{(H)Indox}n¼3]Ir(PPh3)-
(H2O)](OTf)2 (13), as a three-legged piano stool type
complex including one molecule of solvated CDCl3.
Relevant crystal and data parameters are given in Table
1, and selected bond lengths and angles are presented in
Table 3. The most likely explanation of the formation of
13 is that the triflate ligand of 12 was slowly replaced by
water in the solvent. The ORTEPꢀdrawing of 13 showed
that the stereochemistry was Spꢀl; RIr with the aquo ligand
locating under the benzene ring of the indenyl group and
triphenylphosphine as a more stereodemanding ligand
locating on the side opposite to the benzene ring. The
stereochemistry around the iridium center in 13 is
Scheme 2.
spectrum showed the C@N stretching at 1615 cmꢁ1
,
which was shifted to a lower wave number by ca. 60 cmꢁ1
compared to that of the free ligand, indicating that the
Indox ligand recoordinated to the iridium center in an
g5- and g1-coordination manner. The FAB mass spec-
trum of 10a showed three prominent and significant ions
at m/e 859, 708 and 596 with mass and isotope distri-
bution patterns corresponding to [{ðSÞ-(iPr)Indox}n¼2]-
Ir(PPh3)(OTf)]þ + 1, [[{ðSÞ-(iPr)Indox}n¼2]Ir(PPh3)]þ ) 1
and [{ðSÞ-(iPr)Indox}n¼2]Ir(OTf)]þ, respectively. Since a
new stereogenic center at the iridium is constructed in
this reaction, 10a has potentially four diastereomers [two
isomers from each diastereomer ðSplÞ-8 and ðRplÞ-8]. The
31P NMR spectrum of the reaction mixture before pu-
rification showed only two singlet signals at d 9.3 and 8.7
in a 56:44 ratio. The cationic complex 10a consists of
only two diastereomers and the diastereomer ratio of 10a
was almost the same as that of 8a, indicating that both
diastereomers ðSplÞ-8a and ðRplÞ-8a afford only a single
isomer of 10a. A similar discussion could be applied to
the reaction of 8b or the rhodium complexes 9 with more
than 2 equiv. of AgOTf. Under similar conditions, each
diastereomer of these complexes gave a single isomer of
the corresponding cationic complexes 10b and 11.
Reaction of 5, which has no chiral substituent in the
oxazoline ring, with PPh3 and more than 2 equiv. of
AgOTf, successively afforded [g5:g1-[{(H)Indox}n¼3]-
Ir(PPh3)(OTf)]OTf (12) in 65% isolated yield as a yellow
powder (Eq. (3)). All spectral data including the IR
spectroscopy with the lower wave number shift of the
C@N stretching to 1633 cmꢁ1 from the free ligand and
the FAB mass spectroscopy with the parent peak of the
cationic part at m/e 830 in addition to the elemental
Fig. 2. ORTEP drawing of 13 showing the 50% probability thermal
clipsoids. Hydrogen atoms are omitted for clarity except H-atoms of
H2O and CHCl3. The inset is the top view of 13. Some atoms are
omitted for clarity.

Y. Kataoka et al. / Inorganica Chimica Acta 357 (2004) 2965–2979
2971
Table 3
these observations, the stereoselectivity of the arising
stereogenic center at the metal by the ligand exchange
reaction of 8 or 9 with more than 2 equiv. of AgOTf
would be explained as follows: In the first iodine ab-
straction step, one of the two prochiral iodides in each
diastereomer is abstracted by 1 equiv. of AgOTf. The
second step, in which the oxazoline ring recoordinated
to the iridium center, proceeds stereoselectively and the
stereogenic center on the metal is determined by the
steric repulsion between the indenyl group and triphe-
nylphosphine. The third step is the stereospecific ligand
exchange reaction of the remaining iodine for the triflate
to afford the single diastereomer of 10 or 11 from each
diastereomer of 8 or 9. The stereochemistry around the
metal center in 10, 11 and 14a would be the configura-
tion that triphenylphosphine locates on the side opposite
to the benzeneꢀring of the indenyl group due to the fact
that 13 with Spl; RꢀIr configuration was obtained by the
steric repulsion between the indenyl group and the tri-
phenylphosphine ligand.
ꢀ
Selected bond lengths (A) and bond angles (°) for 13
Bond lengths
Ir–C1
2.161(9)
2.146(9)
2.172(9)
2.346(9)
2.332(9)
2.312(2)
2.276(6)
2.071(8)
2.32
Ir–C2
Ir–C3
Ir–C4
Ir–C5
Ir–P
Ir1–O2
Ir1–N
O3–H36
O3–C36
O4–H1o2
O4–O2
3.312(14)
1.86(14)
2.6931(10)
Bond angles
P–Ir1–Cp
130.73
119.45
121.34
158.13
171.4
O2–Ir1–Cp
N–Ir1–Cp
O2–H1o2–O4
O3–H36–C36
Cp is the gravimetric center of the cyclopentadienyl part of the
indenyl group.
probably controlled by the steric hindrance of the in-
ꢀ
denyl group. The shorter Ir–N distance [2.071(8) A] and
the narrower N–Ir–Cp angle (121.34°) compared to
those in ðRplÞ-4b and ðSplÞ-4b are based on relief from
the steric repulsion between the substituent in the ox-
azoline ring and the indenyl group. The bond lengths of
ð5Þ
ꢀ
ꢀ
Ir–C4 [2.346(9) A] and Ir–C5 [2.332(9) Aꢃ are longer
than the corresponding value in ðRplÞ-4b and ðSplÞ-4b.
The distortion of the indenyl ring towards g3-coordi-
nation is evident compared to 4b. One of the two
triflate anions is quite close to the aquo ligand and the
solvated CDCl3. The distances between O4 and H1o2
3. Conclusion
We have designed and prepared a series of new Indox
ligands and synthesized iridium and rhodium complexes
bearing these ligands. The oxazoline ring in the Indox
ligand showed unique characters as a hemilabile ligand.
The monocationic complexes having a stereogenic cen-
ter at the metal have been prepared stereoselectively by
the ligand exchange reaction of the neutral complexes
bearing two prochiral iodido ligands with more than 2
equiv. of AgOTf. The stereochemistry around the metal-
centered chirality would be controlled by the planar
chirality arising from the complexation of the Indox li-
gand, though the absolute configuration of stereogenic
centers in a series of the complexes was not determined
by X-ray analysis. We are currently investigating the
stereochemistry of these complexes and will show a
more detailed reaction mechanism in due course.
ꢀ
ꢀ
[1.86(10) A] and O3 and H36 [3.312(14) A] are consis-
tent with a weak interaction by hydrogen bonding.
We observed an interesting intermediate species of
the ligand exchange reaction of 8a. When the complex
8a [ðSplÞ-8a:ðRplÞ-8a ¼ 56:44 or vice versa] reacted with
only 1 equiv. of AgOTf in dichloromethane at room
temperature for 2 h, [g5:g1-[{ðSÞ-(iPr)Indox}n¼2]Ir-
(PPh3)(I)]OTf (14a) was obtained as a brown powder
along with 8a and 10a (Eq. (5)). Although an analyti-
cally pure form of 14a was not obtained due to con-
tamination of 10a, spectroscopic data including the IR
spectroscopy (1613 cmꢁ1 for mC¼N) and the FAB mass
spectroscopy [m/e 837 for [{ðSÞ-(iPr)Indox}n¼2]Ir(PPh3)-
(I)]þ + 1] supported the proposed structure of 14a.
Although the formation of four isomers is possible
similarly to 10a, the 31P NMR spectrum displaying only
two singlet signals at d 4.4 and 0.4 in a 56:44 ratio, which
was almost the same ratio as that of 8a, suggested that
both diastereomers ðSplÞ-8a and ðRplÞ-8a afforded only a
single isomer of 14a. Reaction of 14a in a 56:44 ratio
with 1 equiv. of AgOTf in dichloromethane at room
temperature for 2 h afforded 10a in a 56:44 ratio. From
4. Experimental
4.1. General
All reactions and manipulations were performed un-
der argon by use of standard vacuum line and Schlenk

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Y. Kataoka et al. / Inorganica Chimica Acta 357 (2004) 2965–2979
tube techniques. All melting points were recorded on a
Yanaco MP-52982 and are uncorrected. Infrared spec-
tra were recorded on a JASCO FT/IR-230. Mass spectra
were obtained on a JEOL JMS DX-303HF spectrome-
(1.50 mol/L, 27.5 mL, 41.3 mmol). The resulting solu-
tion was stirred at 0 °C for 4 h and a solution of
4-bromobutanenitrile (3.4 mL, 34.4 mmol) in THF
(10 mL) was added dropwise at 0 °C. The reaction
mixture was stirred for 12 h at room temperature and
quenched with water, and extracted with diethyl ether
(30 mL ꢂ 3). The combined organic layer was dried over
MgSO4, filtered and the solvent was removed in vacuo.
The resulting oil was purified by column chromatogra-
phy on silica gel (eluent: hexane/ethyl acetate ¼ 5/1) to
afford 4-(3-indenyl)butanenitrile in 83% yield (5.18 g,
1
ter. H NMR spectra were recorded on either 270 MHz
on a JEOL JNM-GSX270 or 300 MHz on a Varian
MERCURY 300 spectrometer. Chemical shifts are re-
ported in ppm (dÞ relative to tetramethylsilane and ref-
erenced to the chemical shift of the residual CHCl3 (d
7.26) or CH2Cl2 (d 5.30) resonance. 31P{1H} NMR
spectra were recorded on either 109.25 MHz on a JEOL
JNM-GSX270 or 121.49 MHz on a Varian MERCURY
300 spectrometer, and the chemical shifts are referenced
to external 85% H3PO4. Elemental analyses were re-
corded on a Perkin–Elmer 2400.
Unless otherwise noted, reagents were purchased
from commercial suppliers and used without further
purification. Dichloromethane was distilled from cal-
cium hydride under argon prior to use and other sol-
vents for recrystallization were dried using standard
procedures. Tetrahydrofuran, toluene, hexane and di-
ethyl ether were distilled from sodium benzophenone
ketyl under argon prior to use. Zinc chloride, which was
purchased from Nacalai Tesque, was heated (ca. 250 °C)
under high vacuum for 1 h and was cooled to room
temperature under argon prior to use. Silver triflate
(AgOTf) was purchased from Sigma–Aldrich Co. The
starting materials, [Ir(coe)2Cl]2 and [Rh(C2H4)2Cl]2,
were prepared according to literature methods [14,15].
Column chromatography was performed using silica gel
(230–400 mesh ASTM, Merck Kieselgel 60).
1
28.3 mmol) as a yellow oil. H NMR (CDCl3, dÞ: 2.05
(quintet, J ¼ 7:1 Hz, 2H, –CH2–), 2.40 (t, J ¼ 7:1 Hz,
2H, –CH2–), 2.74 (t, J ¼ 7:1 Hz, 2H, –CH2–), 3.35 (s,
2H, alkane protons of the indene ring), 6.27 (bs, 1H,
olefin proton of the indene ring), 7.18 (t, J ¼ 7:4 Hz, 1H,
indene ring), 7.28 (t, J ¼ 7:1 Hz, 1H, indene ring), 7.36
(d, J ¼ 7:1 Hz, 1H, indene ring), 7.44 (d, J ¼ 6:9 Hz,
1H, indene ring).
4.2.3. ðSÞ-2-{(20-(1-Indenyl)ethyl)}-4-isopropyloxazoline,
[{(S)-(iPr)Indox}n¼2]H (1a)
A solution of 3-(3-indenyl)propanenitrile (1.73 g, 10.3
mmol) in chlolobenzene (3.0 mL) and a solution of
L-valinol (2.0 mL, 18.0 mmol) in chlolobenzene
(7.0 mL) were successively added to zinc chloride
(0.42 g, 3.1 mmol) in the Schlenk tube. The mixture was
heated under reflux for 2 days. The solvent was removed
in vacuo to give an oily residue. The residue was purified
by column chromatography on silica gel (eluent: hexane/
ethyl acetate ¼ 5/1) to give 1a (1.32 g, 5.2 mmol, 50%) as
1
an air-stable yellow oil. H NMR (CDCl3, dÞ: 0.87 (d,
4.2. Preparation of compounds
J ¼ 6:9 Hz, 3H, –CH3), 0.95 (d, J ¼ 6:9 Hz, 3H, –CH3),
1.67–1.82 (m, 1H, –CH(CH3)2), 2.63–2.72 (m, 2H, –
CH2–), 2.85–2.96 (m, 2H, –CH2–), 3.32 (d, J ¼ 1:6 Hz,
2H, alkane protons of the indene ring), 3.86–3.98 (m,
2H, oxazoline), 4.14–4.28 (m, 1H, oxazoline), 6.27 (t,
J ¼ 1:6 Hz, 1H, olefin proton of the indene ring), 7.19
(dt, J ¼ 7:4, 1.1 Hz, 1H), 7.29 (dt, J ¼ 7:4, 1.1 Hz, 1H),
7.38 (d, J ¼ 7:4 Hz, 1H), 7.44 (d, J ¼ 7:4 Hz, 1H).
IR(KBr, neat, cmꢁ1): 770, 985, 1023, 1164, 1363, 1385,
1464, 1672 (mC¼N), 2899, 2958. HRMASS (EI): Calc. for
4.2.1. 3-(3-Indenyl)propanenitrile [16]
To a solution of indene (5.0 mL, 42.9 mmol) in THF
n
(100 mL) at 0 °C was added a hexane solution of BuLi
(1.50 mol/L, 34.3 mL, 51.5 mmol). The resulting solution
was stirred at 0 °C for 3 h and a solution of 3-bromo-
propanenitrile (3.6 mL, 43.4 mmol) in THF (10 mL) was
added dropwise at 0 °C. The reaction mixture was stirred
for 12 h at room temperature and quenched with water,
and extracted with diethyl ether (30 mL ꢂ 3). The com-
bined organic layer was dried over MgSO4, filtered and
the solvent was removed in vacuo. The resulting oil was
purified by column chromatography on silica gel (eluent:
hexane/ethyl acetate ¼ 5/1) to afford 3-(3-indenyl)pro-
panenitrile in 49% yield (3.58 g, 21.1 mmol) as a yellow
oil. 1H NMR (CDCl3, dÞ: 2.70 (t, J ¼ 7:2 Hz, 2H, –CH2–
), 2.85–2.98 (m, 2H, –CH2–), 3.38 (s, 2H, alkane protons
of the indene ring), 6.36 (bs, 1H, olefin proton of the
indene ring), 7.20–7.49 (m, 4H, indene ring).
25
C17H21NO: 255.1623. Found: m/z 255.1642. ½aꢃD )40.2°
(c 0.737, EtOH).
4.2.4. ðSÞ-2-{(30-(1-Indenyl)propyl)}-4-isopropyloxazo-
line, [{(S)-(iPr)Indox}n¼3]H (1b)
A solution of 3-(3-indenyl)butanenitrile (0.49 g,
2.7 mmol) in chlolobenzene (5.0 mL) and a solution of
L-valinol (0.38 mL, 3.4 mmol) in chlolobenzene
(5.0 mL) were successively added to zinc chloride (0.065
g, 0.47 mmol) in the Schlenk tube. The mixture was
heated under reflux for 2 days. The solvent was removed
in vacuo to give an oily residue. The residue was purified
by column chromatography on silica gel (eluent: hexane/
ethyl acetate ¼ 3/1) to give 1b (0.47 g, 1.8 mmol, 65%) as
4.2.2. 4-(3-Indenyl)butanenitrile [16]
To a solution of indene (4.0 mL, 34.3 mmol) in THF
n
(80 mL) at 0 °C was added a hexane solution of BuLi

Y. Kataoka et al. / Inorganica Chimica Acta 357 (2004) 2965–2979
2973
1
1
an air stable yellow oil. H NMR (CDCl3, dÞ: 0.88 (d,
the following reaction. H NMR (CDCl3, dÞ: 0.81 (d,
J ¼ 6:6 Hz, 3H, –CH3, A or B), 0.84 (d, J ¼ 6:9 Hz, 3H,
–CH3, B or A), 0.89 (d, J ¼ 6:9 Hz, 3H, –CH3, B or A),
0.93 (d, J ¼ 6:6 Hz, 3H, –CH3, A or B), 1.14–1.42 (m,
9H, A and B), 1.30–1.67 (m, 12H, A and B), 1.67–1.89
(m, 4H, A and B), 1.84–2.10 (m, 2H, A and B), 2.05–
2.20 (m, 1H, A and B), 2.36–2.77 (m, 4H, A and B),
2.70–3.00 (m, 1H, A and B), 3.74–3.97 (m, 2H, oxazo-
line, A and B), 4.04–4.24 (m, 1H, oxazoline, A and B),
4.96 (t, J ¼ 2:5 Hz, 1H, indene ring, A and B), 5.73 (bs,
1H, indene ring, A and B), 7.05–7.16 (m, 2H, indene
ring, A and B), 7.17–7.26 (m, 1H, indene ring, A and B),
7.24–7.33 (m, 1H, indene ring, A and B). IR[KBr, Film
(CH2Cl2), cmꢁ1]: 735, 807, 910, 1021, 1092, 1260, 1445,
1466, 1669 (mC¼N), 2850, 2922, 2960. MS (FAB): m/z 667
(Mþ), 558 (Mþ ) COE + 1), 447 (Mþ ) 2COE).
J ¼ 6:9 Hz, 3H, –CH3), 0.96 (d, J ¼ 6:9 Hz, 3H, –CH3),
1.70–1.82 (m, 1H, –CH (CH3)2), 2.03 (dt, J ¼ 14:8, 7.7
Hz, 2H, –CH2–), 2.39 (t, J ¼ 7:7 Hz, 2H, –CH2–), 2.57–
2.68 (m, 2H, –CH2–), 3.32 (s, 2H, alkane protons of the
indene ring), 3.84–3.98 (m, 2H, oxazoline), 4.13-4.26 (m,
1H, oxazoline), 6.23 (s, 1H, olefin proton of the indene
ring), 7.18 (t, J ¼ 7:4 Hz, 1H), 7.28 (t, J ¼ 7:1 Hz, 1H),
7.36 (d, J ¼ 7:1 Hz, 1H), 7.44 (d, J ¼ 6:9 Hz, 1H).
IR(KBr, neat, cmꢁ1): 770, 984, 1019, 1364, 1385, 1459,
1670 (mC¼N), 2894, 2957. HRMASS (EI): Calc. for
25
C18H23NO: 269.1779. Found: m/z 269.1815. ½aꢃD )30.4°
(c 0.507, EtOH).
4.2.5. 2-{30-(1-Indenyl)propyl}oxazoline, [{(H)Indox}n¼3
H (2)
]
A solution of 3-(3-indenyl)butanenitrile (1.30 g, 7.1
mmol) in chlolobenzene (7 mL) and a solution of
2-aminoethanol (1.5 mL, 25 mmol) in chlolobenzene
(7 mL) were successively added to zinc chloride (0.53 g,
3.9 mmol) in the Schlenk tube. The mixture was heated
under reflux for 65 h. The solvent was removed in vacuo
to give an oily residue. The residue was extracted with
diethyl ether. The combined diethyl ether solution was
dried over MgSO4; filtered and the solvent was removed
in vacuo. The residue was purified by column chroma-
tography on silica gel (eluent: hexane/ethyl acetate ¼ 3/
1) to give 1c (0.38 g, 1.7 mmol, 23%) as an air-stable
4.2.7. g5-[{(S)-(iPr)Indox}n¼3]Ir(coe)2 (3b)
A solution of 1b (0.42 g, 1.6 mmol) in THF (10 mL)
was added to a suspension of KH (0.09 g, 2.3 mmol) in
THF (10 mL) at 0 °C. The resulting suspension was
stirred at 80 °C for 1 h and added dropwise to a sus-
pension of [IrCl(coe)2]2 (0.70 g, 0.78 mmol) in THF (40
mL) at 0 °C and then warmed to room temperature.
After the reaction mixture was stirred for 18 h, a dark
red-brown solution was obtained and the solvent was
removed in vacuo. The residue was extracted with hex-
anes (30 mL ꢂ 3). The combined hexane extracts were
concentrated in vacuo to afford 3b (1.0 g, 1.5 mmol,
97%) as a brown oil with a mixture of two diastereomers
1
yellow oil. H NMR (CDCl3, dÞ: 1.98–2.11 (m, 2H, –
CH2–), 2.34–2.42 (m, 2H, –CH2–), 2.57–2.68 (m, 2H, –
CH2–), 3.29–3.35 (m, 2H, alkane protons of the indene
ring), 3.77–3.88 (m, 2H, oxazoline), 4.21 (dt, J ¼ 9:1,
0.8 Hz, 2H, oxazoline), 6.20–6.27 (m, 1H, olefin proton
of the indene ring), 7.19 (td, J ¼ 7:4, 1.1 Hz, 1H), 7.23–
7.33 (m, 1H), 7.32–7.40 (m, 1H), 7.41–7.49 (m, 1H).
IR(KBr, neat, cmꢁ1): 720, 771, 914, 953, 986, 1154,
1169, 1230, 1365, 1391, 1458, 1668 (mC¼N), 2881, 2901,
2938, 3016, 3064. HRMASS (EI): Calc. for C15H17NO:
227.1310. Found: m/z 227.1321.
1
A and B (A:B ¼ 1:1 from H NMR). Complete purifi-
cation of 3b was not successful due to high solubility to
solvents, but its purity was satisfactory in the following
reaction. 1H NMR (CDCl3, dÞ: 0.88 (d, J ¼ 6:9 Hz, 3H,
–CH3, A and B), 0.96 (d, J ¼ 6:9 Hz, 3H, –CH3, A and
B), 1.12–1.42 (m, 8H, A and B), 1.26–1.68 (m, 11H, A
and B), 1.58–1.90 (m, 6H, A and B), 1.80–2.06 (m, 4H,
A and B), 2.08–2.20 (m, 1H, A and B), 2.18–2.46 (m,
4H, A and B), 2.50–2.80 (m, 1H, A and B), 3.79–3.96
(m, 2H, oxazoline, A and B), 4.10–4.25 (m, 1H, oxazo-
line, A and B), 4.88–5.01 (m, 1H, indene ring, A and B),
5.64–5.84 (m, 1H, indene ring, A and B), 7.02–7.17 (m,
2H, A and B), 7.15–7.27 (m, 1H, A and B), 7.24–7.33
(m, 1H, A and B). IR[KBr, Film (CH2Cl2), cmꢁ1]: 739,
806, 1020, 1092, 1263, 1384, 1446, 1465, 1669 (mC¼N),
2851, 2921, 2956. MS (FAB): m/z 682 (Mþ + 1), 571
(Mþ ) COE), 459 (Mþ ) 2COE ) 2).
4.2.6. g5-[{(S)-(iPr)Indox}n¼2]Ir(coe)2 (3a)
A solution of 1a (0.33 g, 1.3 mmol) in THF (10 mL)
was added to a brown suspension of KH (0.12 g,
3.1 mmol) in THF (10 mL) at 0 °C. The resulting sus-
pension was stirred at 80 °C for 1 h and added dropwise
to a suspension of [IrCl(coe)2]2 (0.58 g, 0.65 mmol) in
THF (40 mL) at 0 °C and then warmed to room tem-
perature. After the reaction mixture was stirred for 12 h,
a dark red-brown solution was obtained and the solvent
was removed in vacuo. The residue was extracted with
hexanes (30 mL ꢂ 3). The combined hexane extracts
were concentrated in vacuo to afford 3a (0.81 g, 1.2
mmol, 94%) as a brown oil with a mixture of two dia-
4.2.8. g5:g1-[{(S)-(iPr)Indox}n¼2]Ir(I)2 (4a)
A solution of I2 (0.10 g, 0.40 mmol) in diethyl ether
(10 mL) was added to a solution of 3a (0.26 g, 0.39
mmol) in diethyl ether (20 mL) at room temperature and
brown solids were precipitated immediately. After the
reaction mixture was stirred for 14 h, the solution de-
canted and the resulting brown solids were washed with
diethyl ether (10 mL ꢂ 3). The residue was dried in
1
stereomers A and B (A:B ¼ 1:1 from H NMR). Com-
plete purification of 3a was not successful due to high
solubility to solvents, but its purity was satisfactory in

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Y. Kataoka et al. / Inorganica Chimica Acta 357 (2004) 2965–2979
vacuo to afford 4a (0.24 g, 0.35 mmol, 88%) as a brown
powder with a mixture of two diastereomers A and B
stirred at 0 °C for 1 h and added dropwise to a sus-
pension of [IrCl(coe)2]2 (0.22 g, 0.25 mmol) in THF (40
mL) at 0 °C and then warmed to room temperature.
After the reaction mixture was stirred for 18 h, the
solvent was removed in vacuo. The residue was ex-
tracted with hexanes (30 mL ꢂ 3). The combined hexane
extracts were concentrated in vacuo to afford a brown
oil. A solution of I2 (0.10 mg, 0.40 mmol) in diethyl
ether (10 mL) was added to a solution of the brown oil
in diethyl ether (20 mL) at room temperature and brown
solids were precipitated immediately. After the reaction
mixture was stirred for 3 h, the solution decanted and
the resulting brown solids were washed with diethyl
ether (10 mL ꢂ 3). The residue was dried in vacuo to
afford 5 (0.22 g, 0.32 mmol, 67%) as a brown powder.
1H NMR (CDCl3, dÞ: 2.22–2.50 (m, 2H, –CH2–), 2.63
(ddd, J ¼ 15:9, 11.3, 4.4 Hz, 1H, –CHH–), 2.80–3.00 (m,
2H, –CH2–), 3.11–3.29 (m, 1H, oxazoline), 3.41–3.57
(m, 1H, –CHH–), 4.10 (ddd, J ¼ 13:5, 11.3, 8.2 Hz, 1H,
oxazoline), 4.22–4.35 (m, 2H, oxazoline), 5.91 (d,
J ¼ 2:5 Hz, 1H, indene ring), 6.04 (d, J ¼ 2:5 Hz, 1H,
indene ring), 7.30–7.41 (m, 1H, indene ring), 7.42–7.51
(m, 1H, indene ring), 7.52–7.61 (m, 1H, indene ring),
7.67–7.78 (m, 1H, indene ring). 13C{1H} NMR (CDCl3,
dÞ: 22.8 (–CH2–), 26.7 (–CH2–), 27.2 (–CH2–), 60.0
(oxazoline), 68.9 (oxazoline), 85.2 (indene), 100.4 (ind-
ene), 100.6 (indene), 121.6 (indene), 129.3 (indene),
130.2 (indene), 131.4 (indene), 177.3 (oxazoline).
IR(KBr, tablet, cmꢁ1): 803, 1025, 1098, 1261, 1387,
1455, 1633 (mC¼N), 2853, 2925, 2960. MS (FAB): m/z 673
(Mþ), 546 (Mþ ) I). Anal. Calc. for C15H16I2IrNO: C,
26.80; H, 2.40; N, 2.08. Found: C, 28.59; H, 2.55; N,
2.01%.
1
1
(A:B ¼ 1:1 from H NMR). H NMR (CDCl3, dÞ: 0.69
(d, J ¼ 6:9 Hz, 3H, –CH3, A), 0.71(d, J ¼ 7:1 Hz, 3H,
–CH3, B), 0.72 (d, J ¼ 6:9 Hz, 3H, –CH3, A and B), 1.88
(qqd, J ¼ 7:1, 7.1, 2.2 Hz, 1H, B), 2.44 (qqd, J ¼ 6:9,
6.9, 2.5 Hz, 1H, A), 2.43–2.88 (m, 2H, A and B), 3.04–
3.46 (m, 2H, A and B), 4.05–4.14 (m, 1H, oxazoline, A),
4.16–4.24 (m, 1H, oxazoline, B), 4.27 (t, J ¼ 9:3 Hz, 1H,
oxazoline, B), 4.33 (t, J ¼ 9:1 Hz, 1H, oxazoline, A),
4.40–4.49 (m, 1H, oxazoline, A and B), 5.83 (dd,
J ¼ 2:2, 0.6 Hz, 1H, indene ring, A or B), 5.86 (d,
J ¼ 2:2 Hz, 1H, indene ring, B or A), 5.93 (d, J ¼ 2:2
Hz, 1H, indene ring, A or B), 6.01 (d, J ¼ 2:2 Hz, 1H,
indene ring, B or A), 7.15–7.47 (m, 3H, A and B), 7.49–
7.59 (m, 1H, A and B). IR(KBr, tablet, cmꢁ1): 738, 751,
1013, 1196, 1253, 1387, 1398, 1430, 1458, 1478, 1632
(mC¼N), 2869, 2926, 2958. MS (FAB): m/z 701 (Mþ), 574
(Mþ ) I). Anal. Calc. for C17H20I2IrNO: C, 29.15; H,
2.88; N, 2.00. Found: C, 28.73; H, 2.77; N, 1.83%.
4.2.9. g5:g1-[{(S)-(iPr)Indox}n¼3]Ir(I)2 (4b)
A solution of I2 (72 mg, 0.28 mmol) in diethyl ether
(10 mL) was added to a solution of 3b (0.17 g, 0.24 mmol)
in diethyl ether (20 mL) at room temperature and brown
solids were precipitated immediately. After the reaction
mixture was stirred for 2 h, the solution decanted and the
resulting brown solids were washed with diethyl ether (10
mL ꢂ 3). The residue was dried in vacuo to afford 4b
(0.18 g, 0.25 mmol, >99%) as a brown powder with a
mixture of two diastereomers A and B (A:B ¼ 1:1 from
1
1H NMR). H NMR (CDCl3, dÞ: 0.54 (d, J ¼ 6:9 Hz,
3H, –CH3, A), 0.63 (d, J ¼ 6:9 Hz, 3H, –CH3, A), 0.75
(d, J ¼ 6:9 Hz, 3H, –CH3, B), 0.79 (d, J ¼ 7:1 Hz, 3H,
–CH3, B), 0.86–1.03 [m, 1H, –CH (CH3)2, A], 2.00–2.36
[m, 1H (A or B) + 2H (B or A)], 2.29–2.53 [m 1H
–CH(CH3)2 B + 1H (B or A)], 2.48–2.72 (m, 2H, A or B),
2.74–2.96 (m, 2H, B or A), 2.94–3.09 (m, 1H, A or B),
3.13–3.27 (m, 1H, A or B), 3.30–3.49 [m, 1H (A or B) +
1H (B or A)], 4.04–4.17 (m, 1H oxazoline A + 2H ox-
azoline B), 4.25 (dd, J ¼ 9:1, 3.6 Hz, 1H, oxazoline, A),
4.35 (d, J ¼ 5:8 Hz, 1H, oxazoline, B), 4.41–4.52 (m, 1H,
oxazoline, A), 5.77 (d, J ¼ 2:5 Hz, 1H, indene ring, B),
5.82 (d, J ¼ 2:5 Hz, 1H, indene ring, A), 6.17 (d, J ¼ 2:5
Hz, 1H, indene ring, B), 6.21 (d, J ¼ 2:2 Hz, 1H, indene
ring, A), 7.26–7.77 (m, 4H, A and B). IR(KBr, tablet,
cmꢁ1): 459, 751, 802, 1038, 1084, 1123, 1261, 1385, 1457,
1632 (mC¼N), 2854, 2925, 2957. MS (FAB): m/z 716
(Mþ + 1), 588 (Mþ ) I). Anal. Calc. for C18H22I2IrNO:
C, 30.26; H, 3.10; N, 1.96. Found: C, 30.44; H, 3.09; N,
1.89%.
4.2.11. Preparation of g5-[{(S)-(iPr)Indox}n¼2]Rh-
(C2H4)2 (6a)
A solution of 1a (0.20 g, 0.78 mmol) in THF (30 mL)
was added to a suspension of KH (0.10 g, 2.6 mmol) in
THF (10 mL) at 0 °C. The resulting suspension was
stirred at 0 °C for 1 h and added dropwise to a sus-
pension of [RhCl(C2H4)2]2 (0.16 mg, 0.40 mmol) in
THF (30 mL) at 0 °C and then warmed to room tem-
perature. After the reaction mixture was stirred for 13 h,
a brown solution was obtained and the solvent was re-
moved in vacuo. The residue was extracted with hexanes
(30 mL ꢂ 3). The combined hexane extracts were con-
centrated in vacuo to afford 6a (0.26 g, 0.63 mmol, 79%)
as a brown oil with a mixture of two diastereomers A
and B (A:B ¼ 1:1 from 1H NMR). Complete purification
of 6a was not successful due to high solubility to sol-
vents, but its purity was satisfactory in the following
reaction. 1H NMR (CDCl3, dÞ: 0.84 (d, J ¼ 6:9 Hz, 3H,
–CH3, A or B), 0.86 (d, J ¼ 6:9 Hz, 3H, –CH3, B or A),
0.91 (d, J ¼ 6:9 Hz, 3H, –CH3, B or A), 0.94 (d, J ¼ 6:9
Hz, 3H, –CH3, A or B), 1.58–1.82 (m, 1H, A and B),
1.77–2.02 (m, 4H, A and B), 1.89–2.09 (m, 4H, A and
4.2.10. g5:g1-[{(H)Indox}n¼3]Ir(I)2 (5)
A solution of 2 (0.11 g, 0.48 mmol) in THF (5 mL)
was added to a suspension of KH (37 mg, 0.92 mmol) in
THF (5 mL) at 0 °C. The resulting suspension was

Y. Kataoka et al. / Inorganica Chimica Acta 357 (2004) 2965–2979
2975
B), 2.37–2.75 (m, 4H, A and B), 3.77–4.00 (m, 2H, ox-
azoline, A and B), 4.09–4.26 (m, 1H, oxazoline, A and
B), 5.00 (d, J ¼ 2:7 Hz, 1H, indene ring, A and B), 5.97–
6.09 (m, 1H, indene ring, A and B), 7.07–7.24 (m, 2H, A
and B), 7.19–7.36 (m, 2H, A and B). 13C{1H} NMR
(CD2Cl2, dÞ: 18.4 (–CH3), 19.0 (–CH3), 22.3 (–CH2–),
28.4 (–CH2–), 33.2 [–CH(CH3)2], 45.7 (d, JRh–C ¼ 12:7
Hz, C2H4), 70.4 (oxazoline), 72.8 (oxazoline), 76.9–77.2
(m, indene ring), 92.1–92.4 (m, indene ring), 111.9–112.2
(m, indene ring), 117.7–117.9 (m, indene ring), 120.0
(indene ring), 123.66 (indene ring), 123.72 (indene ring),
166.3 (oxazoline). IR(KBr, neat, cmꢁ1): 742, 804, 914,
983, 1021, 1209, 1258, 1330, 1384, 1433, 1464, 1667
(mC¼N), 2926, 2957, 3059. MS (FAB): m/z 357
[Mþ ) (C2H4)2].
mmol) in diethyl ether (10 mL) at room temperature and
brown solids were precipitated immediately. After the
reaction mixture was stirred for 1 h, the solution de-
canted and the resulting brown solids were washed with
diethyl ether (10 mL ꢂ 3). The residue was dried in va-
cuo to afford 7a (0.35 g, 0.57 mmol, 83%) as a brown
powder with a mixture of two diastereomers A and B
1
1
(A:B ¼ 1:1 from H NMR). H NMR (CDCl3, dÞ: 0.62
(d, J ¼ 6:9 Hz, 3H, –CH3, B), 0.67 (d, J ¼ 7:1 Hz, 3H, –
CH3, A), 0.69 (d, J ¼ 7:1 Hz, 3H, –CH3, A), 0.70 (d,
J ¼ 6:9 Hz, 3H, –CH3, B), 1.89 (qqd, J ¼ 7:1, 7.1, 2.5
Hz, 1H, –CH(CH3)2, B), 2.28 (qqd, J ¼ 7:1, 7.1, 2.5 Hz,
1H, –CH(CH3)2, A), 2.60–2.84 (m, 2H, A and B), 3.05–
3.20 (m, 1H, A and B), 3.24–3.40 (m, 1H, B), 3.47–3.67
(m, 1H, A), 3.89–4.02 (m, 1H, oxazoline, A and B), 4.20
(t, J ¼ 9:1 Hz, 1H, oxazoline, B), 4.29 (t, J ¼ 9:1 Hz,
1H, oxazoline, A), 4.35–4.46 (m, 1H, oxazoline, A and
B), 5.48 (t, J ¼ 2:7 Hz, 1H, indene ring, A and B), 5.93
(d, J ¼ 2:5 Hz, 1H, indene ring, B), 5.99 (d, J ¼ 2:2 Hz,
1H, indene ring, A), 7.20–7.34 (m, 1H, indene ring, A
and B), 7.39–7.66 (m, 3H, indene ring, A and B).
IR(KBr, tablet, cmꢁ1): 454, 742, 754, 806, 952, 976,
1015, 1113, 1139, 1165, 1194, 1250, 1283, 1386, 1397,
1430, 1458, 1478, 1526, 1636 (mC¼N), 2869, 2958, 3074.
MS (FAB): m/z 611 (Mþ), 484 (Mþ ) I). Anal. Calc. for
C17H20I2NORh: C, 33.41; H, 3.30; N, 2.29. Found: C,
32.98; H, 2.95; N, 2.12%.
4.2.12. g5-[{(S)-(iPr)Indox}n¼3]Rh(C2H4)2 (6b)
A solution of 1b (0.14 g, 0.52 mmol) in THF (8 mL) was
added to a suspension of KH (58 mg, 1.4 mmol) in THF
(10 mL) at 0 °C. The resulting suspension was stirred at 80
°C for 1 h and added dropwise to a suspension of
[RhCl(C2H4)2]2 (0.10 mg, 0.26 mmol) in THF (10 mL) at 0
°C and then warmed to room temperature. After the re-
action mixture was stirred for 13 h, a brown solution was
obtained and the solvent was removed in vacuo. The
residue was extracted with hexanes (30 mL ꢂ 3). The
combined hexane extracts were concentrated in vacuo to
afford 6b (0.19 mg, 0.44 mmol, 85%) as a brown oil.
Complete purification of 6b was not successful due to high
solubility to solvents, but its purity was satisfactory in the
following reaction. 1H NMR (CD2Cl2, dÞ: 0.89 (d, J ¼ 6:6
Hz, 3H, –CH3, A and B), 0.96 (d, J ¼ 6:9 Hz, 3H, –CH3,
A and B), 1.62–1.78 (m, 1H, A and B), 1.82–1.98 (m, 5H,
A and B), 1.92–2.09 (m, 5H, A and B), 2.11–2.48 (m, 4H,
A and B), 3.79–3.96 (m, 2H, oxazoline, A and B), 4.12–
4.25 (m, 1H, oxazoline, A and B), 5.04 (d, J ¼ 2:7 Hz, 1H,
indene ring, A and B), 6.02–6.09 (m, 1H, indene ring, A
and B), 7.10–7.22 (m, 2H, A and B), 7.29–7.39 (m, 2H, A
and B). 13C{1H} NMR (CD2Cl2, dÞ: 18.5 (–CH3), 19.0 (–
CH3), 25.0 (–CH2–), 26.3 (–CH2–), 28.1 (–CH2–), 33.2
[–CH(CH3)2], 45.6 (d, JRh–C ¼ 13:2 Hz, C2H4), 70.3 (ox-
azoline), 72.8 (oxazoline), 76.9 (d, J ¼ 4:6 Hz, indene
ring), 92.2 (d, J ¼ 5:8 Hz, indene ring), 92.3 (d, J ¼ 5:8
Hz, indene ring), 93.99 (d, J ¼ 4:0 Hz, indene ring), 94.02
(d, J ¼ 4:0 Hz, indene ring), 112.0–112.2 (m, indene ring),
117.9–118.1 (m, indene ring), 120.0 (indene ring), 123.5
(indene ring), 123.7 (indene ring), 166.7 (oxazoline).
IR(KBr, neat, cmꢁ1): 742, 986, 1199, 1209, 1431, 1459,
1670 (mC¼N), 2958, 3058. MS (FAB): m/z 371
[Mþ ) (C2H4)2]. Anal. Calc. for C22H30NORh: C, 61.83;
H, 7.08; N, 3.28. Found: C, 62.56; H, 7.25; N, 3.22%.
4.2.14. g5:g1-[{(S)-(iPr)Indox}n¼3]Rh(I)2 (7b)
A solution of I2 (80 mg, 0.32 mmol) in diethyl ether
(10 mL) was added to a solution of 6b (0.13 g, 0.30
mmol) in diethyl ether (10 mL) at room temperature and
brown solids were precipitated immediately. After the
reaction mixture was stirred for 24 h, the solution de-
canted and the resulting brown solids were washed with
diethyl ether (10 mL ꢂ 3). The residue was dried in va-
cuo to afford 7b (0.15 g, 0.23 mmol, 77%) as a brown
powder with a mixture of two diastereomers A and B
1
1
(A:B ¼ 1:1 from H NMR). H NMR (CDCl3, dÞ: 0.52
(d, J ¼ 6:9 Hz, 3H, –CH3, A), 0.60 (d, J ¼ 6:9 Hz, 3H, –
CH3, A), 0.63 (d, J ¼ 6:9 Hz, 3H, –CH3, B), 0.68 (d,
J ¼ 6:9 Hz, 3H, –CH3, B), 0.93–1.07 (m, 1H, A), 2.20–
2.55 (m, 2H A, 3H B), 2.58–3.05 (m, 3H, A and B), 3.38–
3.47 (m, 1H, A and B), 3.69 (dt, J ¼ 9:1, 2.8 Hz, 1H,
oxazoline, B), 3.93 (t, J ¼ 8:8 Hz, 1H, oxazoline, B),
3.99–4.10 (m, 1H, oxazoline, A), 4.14–4.25 (m, 2H, ox-
azoline, A), 4.29 (dd, J ¼ 8:8, 3.0 Hz, 1H, oxazoline, B),
5.57 (d, J ¼ 2:7 Hz, 1H, indene ring, A), 5.78 (d, J ¼ 2:7
Hz, 1H, indene ring, B), 5.81 (d, J ¼ 2:5 Hz, 1H, indene
ring, B), 6.08 (d, J ¼ 2:5 Hz, 1H, indene ring, A), 7.27–
7.59 (m, 3H, indene ring, A and B), 7.76–7.86 (m, 1H,
indene ring, A and B). IR(KBr, tablet, cmꢁ1): 523, 754,
1241, 1385, 1435, 1462, 1637 (mC¼N), 2957. MS (FAB):
m/z 626 (Mþ + 1), 498 (Mþ ) I), 371 (Mþ ) 2I). Anal.
Calc. for C18H22I2NORh: C, 34.59; H, 3.55; N, 2.24.
Found: C, 34.11; H, 3.87; N, 2.21%.
4.2.13. g5:g1-[{(S)-(iPr)Indox}n¼2]Rh(I)2 (7a)
A solution of I2 (0.18 g, 0.70 mmol) in diethyl ether
(15 mL) was added to a solution of 6a (0.29 g, 0.70

2976
Y. Kataoka et al. / Inorganica Chimica Acta 357 (2004) 2965–2979
4.2.15. g5-[{(S)-(iPr)Indox}n¼2]Ir(PPh3)(I)2 (8a)
Triphenylphosphine (22 mg, 0.085 mmol) was added
to a solution of 4a (49 mg, 0.070 mmol) as a 1:1 mixture
of diastereomers in THF (10 mL). The reaction mixture
was stirred for 3 h and the solvent was concentrated
in vacuo. The 31P NMR spectrum showed that 8a was a
1:1 mixture of two diastereomers. Recrystallization from
toluene and hexanes gave 8a (55 mg, 0.057 mmol, 82%)
as a brown powder with a mixture of two diastereomers
A and B (A:B ¼ 55:45 from 31P NMR). 1H NMR
(CD2Cl2, dÞ: 0.76 (d, J ¼ 6:9 Hz, 3H, –CH3, A), 0.79 (d,
J ¼ 6:6 Hz, 3H, –CH3, B), 0.81 (d, J ¼ 6:6 Hz, 3H, –
CH3, A), 0.85 (d, J ¼ 6:6 Hz, 3H, –CH3, B), 1.39–1.63
(m, 1H, A and B), 2.12–2.28 (m, 1H, A and B), 2.27–
2.41 (m, 1H, A and B), 2.43–2.59 (m, 1H, A and B),
3.12–3.27 (m, 1H, A and B), 3.60–3.84 (m, 2H, oxazo-
line, A and B), 4.02–4.15 (m, 1H, oxazoline, A and B),
4.84 (t, J ¼ 2:2 Hz, 1H, indene ring, A), 4.87 (t, J ¼ 2:2
Hz, 1H, indene ring, B), 5.45 (d, J ¼ 2:2 Hz, 1H, indene
ring, A), 5.47 (d, J ¼ 2:2 Hz, 1H, indene ring, B), 7.11–
7.29 (m, 1H, A and B), 7.35–7.53 (m, 9H, A and B),
7.47–7.60 (m, 3H, A and B), 7.63–7.79 (m, 6H, A and
B). 31P{1H} NMR (CD2Cl2, dÞ: 1.57 (s, B), 1.60 (s, A).
IR(KBr, tablet, cmꢁ1): 502, 513, 536, 695, 748, 1093,
1435, 1482, 1669 (mC¼N), 2926, 2958, 3057. MS (FAB):
m/z 964 (Mþ + 1), 836 (Mþ ) I), 708 (Mþ ) 2I ) 1), 574
(Mþ ) PPh3 ) I). Anal. Calc. for C35H35I2IrNOP: C,
43.67; H, 3.66; N, 1.45. Found: C, 43.95; H, 3.48; N,
1.32%.
(Mþ ) 2I ) 1), 588 (Mþ ) PPh3 ) I). Anal. Calc. for
C36H37I2IrNOP: C, 44.27; H, 3.82; N, 1.43. Found: C,
44.23; H, 3.65; N, 1.39%.
4.2.17. Preparation of g5-[{(S)-(iPr)Indox}n¼2]Rh-
(PPh3)(I)2 (9a)
Triphenylphosphine (82 mg, 0.31 mmol) was added
to a solution of 7a (0.19 g, 0.31 mmol) as a 1:1 mixture
of diastereomers in THF (10 mL). The reaction mixture
was stirred for 2 h and the solvent was concentrated in
vacuo. The 31P NMR spectrum showed that 9a was a 1:1
mixture of two diastereomers. Recrystallization from
toluene and hexanes gave 9a (0.17 g, 0.20 mmol, 64%) as
a brown powder with a mixture of two diastereomers A
and B (A:B ¼ 55:45 from 31P NMR). 1H NMR (CDCl3,
dÞ: 0.74 (d, J ¼ 6:6 Hz, 3H, –CH3, A), 0.80 (d, J ¼ 6:9
Hz, 3H, –CH3, B), 0.81 (d, J ¼ 6:6 Hz, 3H, –CH3, A),
0.86 (d, J ¼ 6:6 Hz, 3H, –CH3, B), 1.48 (qqd, J ¼ 6:6,
6.6, 6.6 Hz, 1H, –CH(CH3)2, A), 1.60 (qqd, J ¼ 6:6, 6.6,
6.6 Hz, 1H, –CH(CH3)2, B), 2.20–2.56 (m, 3H, –CH2–,
A and B), 3.24–3.40 (m, 1H, –CH2–, A and B), 3.64–3.81
[m, 2H (oxazoline, A) and 1H (oxazoline, B)], 3.81 (t,
J ¼ 8:0 Hz, 1H, oxazoline, B), 4.02–4.15 (m, 1H, oxaz-
oline, A and B), 4.90–4.94 (m, 1H, indene ring, B), 4.93–
4.98 (m, 1H, indene ring, A), 5.26–5.30 (m, 1H, indene
ring, A and B), 7.28–7.53 (m, 11H, A and B), 7.52–7.60
(m, 1H, A and B), 7.66–7.85 (m, 7H, A and B). 31P{1H}
NMR (CDCl3, d): 47.9 (d, JRh–P ¼ 153 Hz, B), 48.0 (d,
JRhꢁP ¼ 155 Hz, A). 31P{1H} NMR (CD2Cl2, dÞ: 48.1
(d, JRh–P ¼ 155 Hz, B), 48.2 (d, JRh–P ¼ 155 Hz, A).
IR(KBr, tablet, cmꢁ1): 499, 512, 528, 695, 748, 1092,
1434, 1480, 1669 (mC¼N), 2958, 3057. MS (FAB): m/z 874
(Mþ + 1), 746 (Mþ ) I), 619 (Mþ ) 2I), 484
(Mþ ) PPh3 ) I). Anal. Calc. for C35H35I2NOPRh: C,
48.13; H, 4.04; N, 1.60. Found: C, 48.17; H, 3.94; N,
1.54%.
4.2.16. g5-[{(S)-(iPr)Indox}n¼3]Ir(PPh3)(I)2 (8b)
Triphenylphosphine (26 mg, 0.098 mmol) was added
to a solution of 4b (57 mg, 0.080 mmol) as a 1:1 mixture
of two diastereomers in THF (10 mL). The reaction
mixture was stirred for 3 h and the solvent was con-
centrated in vacuo. The 31P NMR spectrum showed that
8b was a 1:1 mixture of two diastereomers. Recrystalli-
zation from toluene and hexanes gave 8b (66 mg, 0.067
mmol, 85%) as a brown powder with a mixture of two
diastereomers A and B (A:B ¼ 51:49 from 31P NMR).
1H NMR (CD2Cl2, dÞ: 0.838 (d, J ¼ 6:6 Hz, 3H, –CH3,
A), 0.843 (d, J ¼ 6:6 Hz, 3H, –CH3, B), 0.91 (d, J ¼ 6:9
Hz, 3H, –CH3, A), 0.92 (d, J ¼ 6:6 Hz, 3H, –CH3, B),
1.53–1.77 (m, 2H, A and B), 1.74–1.90 (m, 1H, A and
B), 1.86–2.05 (m, 1H, A and B), 2.07–2.25 (m, 2H, A
and B), 3.03–3.16 (m, 1H, A and B), 3.62–3.96 (m, 2H,
oxazoline, A), 3.86 (t, J ¼ 8:0 Hz, 2H, oxazoline, B),
4.12 (dd, J ¼ 9:1, 8.0 Hz, 1H, oxazoline, A), 4.17 (dd,
J ¼ 9:3, 8.2 Hz, 1H, oxazoline, B), 4.74 (t, J ¼ 2:5 Hz,
1H, indene ring, B), 4.80 (t, J ¼ 2:5 Hz, 1H, indene ring,
A), 5.40–5.47 (m, 1H, indene ring, A and B), 7.36–7.64
(m, 13H, A and B), 7.66–7.80 (m, 6H, A and B).
31P{1H} NMR (CD2Cl2, dÞ: 1.58 (s, B or A), 1.60 (s, A
or B). IR(KBr, Film (CH2Cl2), cmꢁ1): 502, 513, 536,
695, 748, 1093, 1264, 1435, 1481, 1668 (mC¼N), 2958,
3056. MS (FAB): m/z 978 (Mþ + 1), 850 (Mþ ) I), 722
4.2.18. Preparation of g5-[{(S)-(iPr)Indox}n¼3]Rh-
(PPh3)(I)2 (9b)
Triphenylphosphine (26 mg, 0.10 mmol) was added
to a solution of 7b (59 mg, 0.088 mmol) as a 1:1 mixture
of two diastereomers in THF (10 mL). The reaction
mixture was stirred for 2 h and the solvent was con-
centrated in vacuo. The 31P NMR spectrum showed that
9b was a 1:1 mixture of two diastereomers. Recrystalli-
zation from toluene and hexanes gave 9b (46 mg, 0.052
mmol, 59%) as a brown powder with a mixture of two
diastereomers A and B (A:B ¼ 51:49 from 31P NMR).
1H NMR (CD2Cl2, dÞ: 0.85 (d, J ¼ 6:9 Hz, 3H, –CH3, A
and B), 0.92 (d, J ¼ 6:9 Hz, 3H, –CH3, A and B), 1.53–
1.84 (m, 2H, A and B), 1.74–2.04 (m, 2H, A and B),
2.07–2.32 (m, 2H, A and B), 3.10–3.23 (m, 1H, A and
B), 3.70–3.88 (m, 1H, oxazoline, A and B), 3.84–3.94 (m,
1H, oxazoline, A and B), 4.17 (dt, J ¼ 11:0, 8.5 Hz, 1H,
oxazoline, A and B), 4.82–4.88 (m, 1H, indene ring, B),
4.86–4.93 (m, 1H, indene ring, A), 5.29–5.34 (m, 1H,

Y. Kataoka et al. / Inorganica Chimica Acta 357 (2004) 2965–2979
2977
indene ring, A and B), 7.29–7.57 (m, 11H, A and B),
7.56–7.64 (m, 1H, A and B), 7.66–7.85 (m, 7H, A and
B). 31P{1H} NMR (CD2Cl2, dÞ: 48.3 (d, JRh–P ¼ 155 Hz,
B), 48.4 (d, JRh–P ¼ 155 Hz, A). IR(KBr, tablet, cmꢁ1):
499, 511, 528, 694, 748, 1092, 1434, 1480, 1667 (mC¼N),
2957, 3056. MS (FAB): m/z 888 (Mþ + 1), 760 (Mþ ) I),
626 (Mþ ) PPh3 + 1), 498 (Mþ ) PPh3 ) I), 371
(Mþ ) PPh3 ) 2I). Anal. Calc. for C36H37I2NOPRh: C,
48.73; H, 4.20; N, 1.58. Found: C, 48.44; H, 3.98; N,
1.56%.
diastereomers. Recrystallization from CH2Cl2 and hex-
anes gave 9b (20 mg, 0.020 mmol, 58%) as a yellow
powder with a mixture of two diastereomers A and B
1
(A:B ¼ 53:47 from 31P NMR). H NMR (CD2Cl2, dÞ:
0.55 (d, J ¼ 6:6 Hz, 3H, –CH3, A), 0.59 (d, J ¼ 6:9 Hz,
3H, –CH3, B), 0.65 (d, J ¼ 6:9 Hz, 3H, –CH3, B), 0.86
(d, J ¼ 6:9 Hz, 3H, –CH3, A), 1.16–1.35 (m, 1H, –
CH(CH3)2, A), 1.80–2.00 (m, 1H, –CH(CH3)2–, B),
2.00–2.53 [m, 5H (A) + 6H (B)], 2.57–2.75 (m, 1H, –
CHH–, A), 2.94 (dt, J ¼ 8:8, 3.3 Hz, 1H, oxazoline, B),
3.84 (dt, J ¼ 8:5, 1.9 Hz, 1H, oxazoline, B), 3.93 (t,
J ¼ 9:3 Hz, 1H, oxazoline, B), 4.14 (t, J ¼ 9:3 Hz, 1H,
oxazoline, B), 4.37 (dd, J ¼ 9:3, 3.0 Hz, 1H, oxazoline,
A), 4.49 (dd, J ¼ 9:3, 3.3 Hz, 1H, oxazoline, B), 5.88
(dd, J ¼ 3:3, 2.7 Hz, 1H, indene ring, B), 5.95 (t, J ¼ 2:7
Hz, 1H, indene ring, A), 6.34 (d, J ¼ 2:5 Hz, 1H, indene
ring, A), 6.60 (d, J ¼ 1:9 Hz, 1H, indene ring, B), 7.04–
7.98 (m, 17H, A and B), 7.70–8.10 [m, 2H (A) + 1H (B)],
8.19 (d, J ¼ 8:2 Hz, 1H, B). 31P{1H} NMR (CD2Cl2, dÞ:
8.9 (s, B), 9.4 (s, A). IR(KBr, tablet, cmꢁ1): 516, 537,
638, 696, 754, 1033, 1094, 1169, 1230, 1261, 1436, 1626
(mC¼N), 2926, 2965, 3063. MS (FAB): m/z 873 (Mþ + 1),
723 (Mþ ) OTf), 610 (Mþ ) PPh3). Anal. Calc. for
C38H37F6IrNO7PS2: C, 44.70; H, 3.65; N, 1.37. Found:
C, 44.54; H, 3.89; N, 1.39%.
4.2.19. [g5:g1-[{(S)-(iPr)Indox}n¼2]Ir(PPh3)(OTf)]-
OTf (10a)
AgOTf (17 mg, 0.066 mmol) was added to a solution
of 8a (28 mg, 0.029 mmol) as a 55:45 mixture of two
diastereomers in CH2Cl2 (5 mL) at room temperature.
The reaction mixture was stirred for 3 h to afford a
yellow suspension. After removal of a brown precipi-
tate, the solution was concentrated in vacuo. The 31P
NMR spectrum showed that 10a was a 56 : 44 mixture
of two diastereomers. Recrystallization from CH2Cl2
and hexanes gave 10a (24 mg, 0.024 mmol, 82%) as a
yellow brown powder with a mixture of two diastereo-
1
mers A and B (A:B ¼ 56:44 from 31P NMR). H NMR
(CDCl3, dÞ: 0.42 (d, J ¼ 7:1 Hz, 3H, –CH3, A), 0.47 (d,
J ¼ 6:9 Hz, 3H, –CH3, A), 0.63 (d, J ¼ 7:1 Hz, 3H,
–CH3, B), 0.67 (d, J ¼ 6:6 Hz, 3H, –CH3, B), 1.13–1.33
(m, 1H, –CH(CH3)2, A), 1.68–1.90 (m, 2H, B), 1.88–
2.09 (m, 2H, –CHH–, A), 2.52–2.69 [m, 1H (oxazoline,
A) and 1H (–CHH–, B)], 2.70–2.91 (m, 2H, A), 3.20–
3.40 (m, 2H, B), 3.59 (t, J ¼ 9:1 Hz, 1H, oxazoline, A),
3.54–3.78 (m, 1H, –CHH–, B), 4.23 (dd, J ¼ 9:3, 2.3 Hz,
1H, oxazoline, A), 4.24–4.43 (m, 1H, oxazoline, B),
4.46–4.59 (m, 1H, oxazoline, B), 4.95–5.03 (m, 1H,
indene ring, A), 5.88–5.98 (m, 1H, indene ring, B), 6.18–
6.28 (m, 1H, indene ring, B), 6.48 (d, J ¼ 2:2 Hz, 1H,
indene ring, A), 7.38–7.73 (m, 15H, A and B), 7.79–7.91
(m, 2H, A and B), 7.88–8.00 (m, 2H, A and B). 31P{1H}
NMR (CDCl3, dÞ: 8.7 (s, B), 9.3 (s, A). 31P{1H} NMR
(CD2Cl2, dÞ: 8.46 (s), 8.51 (s). IR(KBr, tablet, cmꢁ1):
463, 516, 535, 576, 638, 696, 755, 988, 1032, 1094, 1168,
1259, 1437, 1483, 1615 (mC¼N), 2930, 2966, 3061. MS
(FAB): m/z 859 (Mþ + 1), 708 (Mþ ) OTf ) 1), 596
(Mþ ) PPh3). Anal. Calc. for C37H35F6IrNO7PS2: C,
44.13; H, 3.50; N, 1.39. Found: C, 43.79; H, 3.75; N,
1.29%.
4.2.21. [g5:g1-[{(S)-(iPr)Indox}n¼2]Rh(PPh3)(OTf)]-
OTf (11a)
AgOTf (22 mg, 0.085 mmol) was added to a solution
of 9a (26 mg, 0.030 mmol) as a 57:43 mixture of dia-
stereomers in CH2Cl2 (8.0 mL) at room temperature.
The reaction mixture was stirred for 2 h to afford a dark
red suspension. After removal of a brown precipitate,
the solution was concentrated in vacuo. The 31P NMR
spectrum showed that 11a was a 57 : 43 mixture of
diastereomers. Recrystallization from CH2Cl2 and hex-
anes gave 11a (17 mg, 0.018 mmol, 61%) as an orange
powder with a mixture of two diastereomers A and B
1
(A:B ¼ 59:41 from 31P NMR). H NMR (CD2Cl2, dÞ:
0.43 (d, J ¼ 7:1 Hz, 3H, –CH3, A), 0.44 (d, J ¼ 6:9 Hz,
3H, –CH3, A), 0.64 (d, J ¼ 6:9 Hz, 3H, –CH3, B), 0.71
(d, J ¼ 6:6 Hz, 3H, –CH3, B), 1.13–1.30 (m, 1H, –CHH–
, A), 1.36 (qqd, J ¼ 6:9, 6.9, 2.2 Hz, 1H, –CH(CH3)2,
A), 1.61–1.85 (m, 1H, –CH(CH3)2, B), 1.82-2.05 (m, 1H,
–CHH–, B), 2.26 (ddd, J ¼ 16:5, 7.2, 2.2 Hz, 1H, –
CHH–, A), 2.44–2.74 [m, 1H (A) and 3H (B)], 3.10–3.28
(m, 1H, –CHH–, A), 3.34–3.50 (m, 1H, oxazoline, B),
3.57–3.74 (m, 1H, –CHH–, A), 3.73 (t, J ¼ 9:1 Hz, 1H,
oxazoline, A), 4.22–4.38 (m, 1H, oxazoline, A and B),
4.46–4.61 (m, 1H, oxazoline, B), 4.99–5.08 (m, 1H,
indene ring, A), 5.83–5.92 (m, 1H, indene ring, B), 5.97–
6.05 (m, 1H, indene ring, B), 6.57 (d, J ¼ 2:5 Hz, 1H,
indene ring, A), 7.42–7.80 (m, 16H, A and B), 7.78–7.92
(m, 1H, A and B), 7.95–8.10 (m, 2H, A and B). 31P{1H}
NMR (CD2Cl2, dÞ: 43.1 (d, JRh–P ¼ 146 Hz, A), 44.6 (d,
JRh–P ¼ 151 Hz, B). IR(KBr, tablet, cmꢁ1): 528, 638,
4.2.20. [g5:g1-[{(S)-(iPr)Indox}n¼3]Ir(PPh3)(OTf)]-
OTf (10b)
AgOTf (18 mg, 0.069 mmol) was added to a solution
of 8b (34 mg, 0.035 mmol) as a 51:49 mixture of dia-
stereomers in CH2Cl2 (5.0 mL) at room temperature.
The reaction mixture was stirred for 2 h to afford a pale
yellow suspension. After removal of a brown precipitate,
the solution was concentrated in vacuo. The 31P NMR
spectrum showed that 10b was a 51 : 49 mixture of

2978
Y. Kataoka et al. / Inorganica Chimica Acta 357 (2004) 2965–2979
696, 803, 1032, 1094, 1172, 1230, 1261, 1437, 1482, 1623
(mC¼N), 2964, 3061. MS (FAB): m/z 768 (Mþ), 619
(Mþ ) OTf), 506 (Mþ ) PPh3), 357 (Mþ ) OTf ) PPh3).
Anal. Calc. for C37H35F6NO7PRhS2: C, 48.43; H, 3.84;
N, 1.53. Found: C, 48.22; H, 3.99; N, 1.58%.
694, 752, 792, 999, 1093, 1161, 1187, 1260, 1435, 1481,
1666 (mC¼N), 2903, 2967, 3056. MS (FAB): m/z 936
(Mþ), 808 (Mþ ) I), 681 (Mþ ) 2I), 546 (Mþ ) PPh3 ) I).
Anal. Calc. for C33H31I2IrNOP: C, 42.41; H, 3.34; N,
1.50. Found: C, 38.20; H, 2.62; N, 1.31%.
4.2.22. [g5:g1-[{(S)-(iPr)Indox}n¼3]Rh(PPh3)(OTf)]-
OTf (11b)
4.2.24. [g5:g1-[{(H)Indox}n¼3]Ir(PPh3)(OTf)]OTf (12)
AgOTf (39 mg, 0.15 mmol) was added to a solution of
[{(H)Indox}n¼3]Ir(PPh3)(I)2 (45 mg, 0.048 mmol), which
was not purified by recrystallization, in CH2Cl2 (5.0 mL)
at room temperature. The reaction mixture was stirred
for 3 h and the solution was concentrated in vacuo.
AgOTf (17 mg, 0.066 mmol) was added to a solution
of 9b (26 mg, 0.030 mmol) as a 51:49 mixture of dia-
stereomers in CH2Cl2 (8.0 mL) at room temperature.
The reaction mixture was stirred for 2 h to afford an
orange suspension. After removal of a brown precipitate
and the solution was concentrated in vacuo. The 31P
NMR spectrum showed that 11b was a 51:49 mixture of
diastereomers. Recrystallization from CH2Cl2 and hex-
anes gave 11b (30 mg, 0.033 mmol, >99%) as an orange
powder with a mixture of two diastereomers A and B
(A:B ¼ 60:40 from 1H and 31P NMR). 1H NMR
(CD2Cl2, dÞ: 0.54 (d, J ¼ 6:3 Hz, 3H, –CH3, A), 0.59 (d,
J ¼ 6:3 Hz, 3H, –CH3, A), 0.65 (d, J ¼ 6:9 Hz, 3H, –
CH3, B), 0.87 (d, J ¼ 6:9 Hz, 3H, –CH3, B), 0.88–1.16
(m, 1H, A and B), 1.73–1.82 (m, 1H, B), 1.90–2.15 (m,
1H, A), 2.00–2.63 (m, 5H, A and B), 2.95–3.10 (m, 1H,
oxazoline, B), 3.64–3.78 (m, 1H, oxazoline, A), 3.89 (t,
J ¼ 9:3 Hz, 1H, oxazoline, B), 4.18 (t, J ¼ 9:3 Hz, 1H,
oxazoline, A), 4.37 (dd, J ¼ 9:9, 3.0 Hz, 1H, oxazoline,
A), 4.47 (dd, J ¼ 9:3, 4.1 Hz, 1H, oxazoline, B), 5.78–
5.84 (m, 1H, indene ring, B), 5.95–5.99 (m, 1H, indene
ring, A), 6.23 (d, J ¼ 2:7 Hz, 1H, indene ring, A), 6.45
(d, J ¼ 2:5 Hz, 1H, indene ring, B), 7.35–7.82 (m, 15H,
A and B), 7.74–7.90 (m, 1H, A and B), 7.91–8.14 [m, 3H
(A) and 2H (B)], 8.18–8.28 (m, 1H, B). 31P{1H} NMR
(CD2Cl2, dÞ: 44.4 (d, JRh–P ¼ 149 Hz, A), 45.3 (d,
JRh–P ¼ 151 Hz, B). IR(KBr, tablet, cmꢁ1): 516, 527,
638, 693, 759, 1033, 1094, 1171, 1260, 1437, 1627 (mC¼N),
2961. MS (FAB): m/z 782 (Mþ), 633 (Mþ ) OTf), 520
(Mþ ) PPh3), 371 (Mþ ) PPh3 ) OTf). Anal. Calc. for
C38H37F6NO7PRhS2: C, 48.99; H, 4.00; N, 1.50. Found:
C, 48.56; H, 4.22; N, 1.49%.
1
The H and 31P NMR showed that 12 was a single di-
astereomer. Recrystallization from CH2Cl2 and hexanes
gave 12 (30 mg, 0.031 mmol, 65%) as a yellow powder.
1H NMR (CDCl3, dÞ: 1.16–1.38 (m, 1H, –CH2–), 2.10–
2.52 (m, 5H, –CH2–), 2.75 (ddd, J ¼ 12:9, 10.2, 10.2 Hz,
1H, oxazoline), 3.50–3.70 (m, 1H, oxazoline), 4.27–4.57
(m, 2H, oxazoline), 5.83 (t, J ¼ 2:5 Hz, 1H, indene), 6.39
(d, J ¼ 2:5 Hz, 1H, indene), 7.33–7.52 (m, 6H), 7.48–
7.69 (m, 9H), 7.66–7.77 (m, 1H), 7.82–7.96 (m, 2H),
7.98–8.09 (m, 1H). 31P{1H} NMR (CDCl3, dÞ: 10.6 (s).
IR(KBr, tablet, cmꢁ1): 502, 517, 536, 642, 696, 756,
1034, 1095, 1171, 1229, 1261, 1436, 1633 (mC¼N), 2927,
3055. MS (FAB): m/z 830 (Mþ), 681 (Mþ ) OTf), 568
(Mþ ) PPh3). Anal. Calc. for C35H31F6IrNO7PS2:
C, 42.94; H, 3.19; N, 1.43. Found: C, 38.05; H, 2.63; N,
1.33%.
4.3. Preparation of single crystals for X-ray analysis
4.3.1. Single crystals of 4b
A solution of I2 (27 mg, 0.10 mmol) in diethyl ether
(35 mL) was added to a solution of 6b (71 g, 0.11 mmol)
in diethyl ether (70 mL) at room temperature. The re-
action mixture was placed at room temperature for 20
days. Colorless single crystals were obtained along with
a brown powder.
4.3.2. Single crystals of 13
A solution of 12 (25 mg) in CDCl3 (ca. 0.8 mL) was
placed in the NMR tube at room temperature for 4 days
to afford just a small amount of yellow single crystals of
13. These crystals were not dissolved in various solvents.
Unfortunately, spectral and physical data could not be
obtained except for the melting point (>210 °C).
4.2.23. g5-[{(H)Indox}n¼3]Ir(PPh3)(I)2
Triphenylphosphine (52 mg, 0.20 mmol) was added
to a solution of 5 (132 mg, 0.20 mmol) in THF (10 mL).
The reaction mixture was stirred for 3 h and the solvent
was concentrated in vacuo. Recrystallization from tol-
uene and hexanes gave g5-[{P(H)Indoxn ¼ 3]Ir(PPh3)(I)2
(46 mg, 0.050 mmol, 25%) as a brown powder. 1H NMR
(CDCl3, dÞ: 1.57–1.81 (m, 2H, –CH2–), 1.84–2.05 (m,
1H, –CH2–), 2.07–2.22 (m, 2H, –CH2–), 2.94–3.14 (m,
1H, –CH2–), 3.70 (t, J ¼ 9:1 Hz, 2H, oxazoline), 3.98–
4.22 (m, 2H, oxazoline), 4.73 (t, J ¼ 2:2 Hz, 1H, indene),
5.44 (d, J ¼ 2:2 Hz, 1H, indene), 7.22–7.35 (m, 1H),
7.29–7.45 (m, 8H), 7.40–7.50 (m, 3H), 7.44–7.57 (m,
1H), 7.61–7.83 (m, 6H). 31P{1H} NMR (CDCl3, dÞ:
1.6(s). IR[KBr, Film (CH2Cl2), cmꢁ1]: 501, 536, 667,
5. Supplementary material
The X-ray crystallographic files, in CIF format, are
available from the Cambridge Crystallographic Data
Centre on quoting the deposition numbers: CCDC
227510 for 4 and CCDC 227511 for 13. Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge CB2 1EZ,

Y. Kataoka et al. / Inorganica Chimica Acta 357 (2004) 2965–2979
2979
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Acknowledgements
This work was supported in part by Grants-in-Aid
for Scientific Research from the Ministry of Education,
Science, Sports and Culture, Japan.
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