A series of multinuclear homo- and heterometallic complexes with bridging tellurolato ligands derived from [Cp*Ir(CO)(TeTol)2] (Cp* = η5-C5Me5, Tol = p-tolyl)

Article abstract of DOI:10.1016/j.jorganchem.2009.09.038

Reactions of [Cp^*Ir(CO)(TeTol)₂] (1; Tol = p-tolyl) with certain organometallic Pd(II), Pt(II), Ir(III), Rh(III), and Ru(II) species afforded IrPd, IrPt, IrPt₂, Ir₂, IrRh, IrRu₃, and IrRu complexes having tellurolato-bridged dinuclear or trinuclear cores. This finding demonstrates that 1 is a versatile precursor to synthesize a variety of multinuclear homo- and heterometallic μ-tellurolato complexes, whose chemistry is still less advanced as compared with that of μ-thiolato complexes.

Full text of DOI:10.1016/j.jorganchem.2009.09.038

Journal of Organometallic Chemistry 695 (2010) 137–144
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
A series of multinuclear homo- and heterometallic complexes with bridging
tellurolato ligands derived from [Cp*Ir(CO)(TeTol)2] (Cp* =
g
5-C5Me5, Tol = p-tolyl)
*
Takafumi Nakagawa, Hidetake Seino, Yasushi Mizobe
Institute of Industrial Science, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8505, Japan
a r t i c l e i n f o
a b s t r a c t
Reactions of [Cp*Ir(CO)(TeTol)2] (1; Tol = p-tolyl) with certain organometallic Pd(II), Pt(II), Ir(III), Rh(III),
and Ru(II) species afforded IrPd, IrPt, IrPt2, Ir2, IrRh, IrRu3, and IrRu complexes having tellurolato-bridged
dinuclear or trinuclear cores. This finding demonstrates that 1 is a versatile precursor to synthesize a vari-
Article history:
Received 12 August 2009
Received in revised form 17 September
2009
Accepted 25 September 2009
Available online 4 October 2009
ety of multinuclear homo- and heterometallic
l-tellurolato complexes, whose chemistry is still less
advanced as compared with that of -thiolato complexes.
l
Ó 2009 Elsevier B.V. All rights reserved.
Keywords:
Iridium
Tellurolato complex
Multinuclear complex
Heterometallic complex
X-ray crystallography
1. Introduction
mediate stage [Cp*Ir(CO)(
l-Te)(l-TeTol)Pt(Tol)(PPh3)] was isolable
from the reaction of 1 with 1 equiv. of [Pt(PPh3)3] (Scheme 1).
Now we have found that when 1 is allowed to react with an
equimolar amount of Pd(II) complex [PdCl2(cod)] (cod = 1,5-cyclo-
octadiene) at room temperature, the tellurolato-bridged heterobi-
In contrast to the extensive studies that are continuing about
the syntheses and reactivities of the alkoxido and thiolato com-
plexes, the chemistry of heavier chalcogenolato, viz. selenolato
and tellurolato complexes is less advanced [1]. Thus, with respect
to the multinuclear complexes with bridging tellurolato ligands,
for example, fully characterized compounds are relatively limited
and those with the heterometallic cores are rare [2]. In this paper,
we wish to describe the synthesis and structures of some new
homometallic and heterobimetallic complexes with bridging
tellurolato ligands derived from the bis(tellurolato) complex
metallic complex [Cp*Ir(CO)(
l-TeTol)2PdCl2] (2) is obtained in
moderate yield (Eq. (1)). The structure of 2 has been determined
by the X-ray crystallography. The ORTEP drawing is shown in
Fig. 1, while the selected interatomic distances and angles are
listed in Table 1.
Cp*
Te
Te
[PdCl (cod) ] (1 equiv)
2
2
[Cp*Ir(CO)(TeTol)2] (1; Cp* =
g
5-C5Me5, Tol = p-tolyl) prepared pre-
Ir
Pd
Cl
Cl
1
viously in this laboratory [3].
THF, r.t.
Tol
Tol
C
O
ð1Þ
2. Results and discussion
2
2.1. Reactions of 1 with Pd(II) and Pt(II) complexes
Complex 2 consists of the Ir and Pd centers with three-legged
piano stool and square planar configurations, respectively, which
are bridged by two TeTol ligands. The Ir–Pd distance at
3.9038(6) Å is indicative of the absence of any bonding interactions
between these two metal centers. The IrPdTe2 core is slightly
folded with the dihedral angle of 165° around the Teꢀ ꢀ ꢀTe vector.
Two Tol groups are mutually syn, which are oriented to the direc-
tion opposite to the bulky Cp* ligand. The Ir–Te, Pd–Te, and Pd–Cl
bond lengths in 2 are not unusual. The 1H NMR spectrum showing
one Cp* resonance at d 2.20 as well as one Me signal due to Tol
In the previous paper [3], we have reported the formation of the
triangular clusters with two capping tellurido ligands [Cp*Ir-
(CO)(l3-Te)2{M(Tol)(PPh3)}2] (M = Pd, Pt) from 1 and 2 equiv. of
[Pd(PPh3)4] or [Pt(PPh3)3]. These reactions proceed via the inser-
tion of M(0) centers into Te–Tol bonds in 1, and the expected inter-
* Corresponding author. Fax: +81 3 5452 6361.
E-mail address: ymizobe@iis.u-tokyo.ac.jp (Y. Mizobe).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.09.038

138
T. Nakagawa et al. / Journal of Organometallic Chemistry 695 (2010) 137–144
Tol
PPh
Cp*
TeTol
TeTol
M
M
3
Cp*
Ir
Te
Te
[Pt(PPh ) ] or [Pd(PPh ) ] (2 equiv)
3 3
3 4
Ir
Tol
PPh
C
THF, r.t.
C
3
O
O
1
M = Pt, Pd
[Pt(PPh ) ]
(1 equiv)
3 3
[Pt(PPh ) ]
3 3
Te
Te
Tol
Cp*
(1 equiv)
Tol
PPh
Ir
Pt
3
C
O
Scheme 1.
groups at d 2.27 is consistent with the solid structure. The m(C„O)
value at 2023 cmꢁ1 is somewhat higher than that in mononuclear 1
at 1982 cmꢁ1 due to the weaker back-donating ability of the Ir cen-
ter in 2 with l-TeTol ligands than that in 1 with the terminal TeTol
ligands.
The reaction of 1 with 1 equiv. of [PtCl2(cod)] was conducted
analogously, yielding the mixture of two products: a dinuclear
complex [Cp*Ir(CO)(
l
-TeTol)2PtCl2] (3) and a trinuclear complex
[{Cp*Ir(CO)(
l-TeTol)2}2Pt]Cl2 (4), the molar ratio of which in the
reaction mixture was estimated to be ca. 5:3 from its 1H NMR spec-
trum (Eq. (2)). Complex 4 was isolated as analytically pure crystals
by recrystallizing the product mixture from DMF–ether, and the
preliminary X-ray analysis disclosed its tellurolato-bridged trinu-
clear structure shown in Eq. (2). On the other hand, purification
of 3 was unsuccessful despite the repeated crystallization of the
evaporated residue of the mother liquor obtained after deposition
of 4 on recrystallization. However, a small amount of single crys-
tals formulated as 3ꢀC2H4Cl2 (C2H4Cl2 = 1,2-dichloroethane) were
obtained during the attempts of purification and its structure could
be determined in detail by the X-ray diffraction (Fig. 2). Selected
bond distances and angles are summarized in Table 1.
Fig. 1. An ORTEP drawing for 2 at 50% probability level. All hydrogen atoms are
omitted for clarity.
Table 1
Selected interatomic distances (Å) and angles (°) in 2 and 3.
2
(a) Distances
Irꢀ ꢀ ꢀPd
3.9038(6)
2.6566(5)
1.858(5)
2.5184(6)
2.371(2)
Ir–Te(1)
Ir–C(11)
Pd–Te(1)
Pd–Cl(1)
Ir–Te(2)
2.6701(4)
1.135(7)
2.5434(6)
2.367(2)
C(11)–O(1)
Pd–Te(2)
Pd–C1(2)
(b) Angles
Te(1)–Ir–Te(2)
Ir–Te(1)–Pd
Ir–Te(1)–C(12)
Pd–Te(1)–C(12)
Te(1)–Pd–Cl(1)
Cl(1)–Pd–Cl(2)
78.98(1)
97.89(2)
100.5(2)
102.2(1)
88.77(4)
96.17(6)
Te(1)–Pd–Te(2)
Ir–Te(2)–Pd
Ir–Te(2)–C(19)
Pd–Te(2)–C(19)
Te(2)–Pd–Cl(2)
Ir–C(11)–O
84.01(2)
96.93(2)
98.7(2)
102.9(2)
91.08(5)
177.7(5)
3
(a) Distances
Irꢀ ꢀ ꢀPt
3.8527(4)
2.6495(4)
1.152(10)
2.351(1)
Ir–Te
Ir–C(7)
Pt–Te
1.860(8)
2.5227(4)
C(7)–O(1)
Pt–Cl
(b) Angles
Te–Ir–Te*
Ir–Te–Pt
81.15(2)
96.27(2)
102.5(1)
93.58(5)
Te–Pt–Te*
Ir–Te(1)–C(1)
Te–Pt–Cl
86.18(2)
103.2(2)
90.10(3)
178.9(7)
Fig. 2. An ORTEP drawing for 3 at 50% probability level. All hydrogen atoms are
omitted for clarity. Crystallographically imposed mirror plane defined by the Ir and
Pt centers as well as the CO ligand is present.
Pt–Te–C(1)
Cl–Pt–Cl*
Ir–C(7)–O

T. Nakagawa et al. / Journal of Organometallic Chemistry 695 (2010) 137–144
139
cis-[Cp*Ir(CO)( -TeTol)2RhCp*Cl][PF6] (60a) was present as the
l
[PtCl (cod) ] (1 equiv)
2
2
1
sole complex in the reaction mixture. Thus, 60a was able to be
isolated as an analytically pure form. The ORTEP drawings of
the cations in 50a, 50b, and 6a were depicted in Figs. 3–5, while
important interatomic distances and angles therein are listed in
Table 2.
THF, r.t.
Cl
2
O
C
Cp*
Tol
Te
Te
Tol
Cl
Cl
Ir
Cp*
Pt
Te
Te
Tol
Ir
Ir
Pt
Te
Tol
C
O
+
Te
Cp*
Tol
As shown in Fig. 3, the solid state structure of 50a consists of
the Ir2Te2 core, which is puckered only slightly with the dihedral
angle between two IrTe2 planes at 172°. The Irꢀ ꢀ ꢀIr separation at
3.964(1) Å indicates the absence of metal–metal bond. The
geometry of the two Cp* ligands is cis with respect to the Ir2Te2
ring, while that of the two Tol groups is syn and oriented to the
direction opposite to the Cp* ligands. Two benzene rings are
close to parallel to the Irꢀ ꢀ ꢀIr vector, minimizing the steric repul-
sion between the Tol group and the CO and Cl ligands as well as
the other Tol ligand.
C
O
Tol
3
4
ð2Þ
The crystal structure of 3 is essentially the same as that of 2, ex-
cept that the IrPtTe2 ring is almost planar with the dihedral angle
of 176° between the IrTe2 and PtTe2 planes around the Teꢀ ꢀ ꢀTe vec-
tor. The Irꢀ ꢀ ꢀPt separation at 3.8527(4) Å is indicative of the ab-
sence of any bonding interactions.
For 4, the preliminary X-ray diffraction study has disclosed its
trinuclear structure shown in Eq. (2). In 4, the Pt atom coincides
with the inversion center and the half of the molecule is crystal-
lographically independent, the core structure of which is analo-
gous to those in 3 and 2. The 1H NMR data as well as the
The solid state structure of 50b is shown in Fig. 4, which clearly
indicates the two Cp* ligands in trans dispositions. The Ir2Te2 ring is
almost planar with the dihedral angle around the Teꢀ ꢀ ꢀTe vector of
174° and the Irꢀ ꢀ ꢀIr distance without metal–metal bond is
3.9742(8) Å. Two Tol groups are syn and oriented to the direction
of the CO ligand. In contrast to 50a, two Tol planes are close to per-
pendicular to the Irꢀ ꢀ ꢀIr vector, presumably because the steric
repulsion against the Cp* ligand is more significant than that to
the other Tol group.
m
(C„O) value for 3 and 4 are diagnostic of these crystal struc-
tures (see Section 3).
2.2. Reactions of 1 with Ir(III) and Rh(III) complexes
The X-ray structure of 6a shown in Fig. 5 is quite similar to that
of 50a, where the Irꢀ ꢀ ꢀRh distance is 3.971(1) Å and the dihedral an-
gle between the IrTe2 and RhTe2 planes is 174°.
Reactions of 1 with 0.5 equiv. of dinuclear Ir(III) and Rh(III)
complexes [(Cp*MCl)2(
l
-Cl)2] were carried out in CH2Cl2 at room
temperature, which afforded the mixtures of the tellurolato-
bridged dinuclear complexes, cis-[Cp*Ir(CO)( -TeTol)2MCp*Cl]Cl
When the isolated crystals of 50a, 50b, and 60a were re-dis-
solved in CDCl3, the NMR spectrum of each complex shows the
presence of two species in solution as summarized in Section 3.
This feature can be interpreted in terms of the equilibration of
syn and anti forms with respect to the two Tol groups in a solu-
tion state, as is ubiquitously observed for the thiolato-bridged
dinuclear cores [4]. The structures of syn and anti forms in equi-
librium are depicted in Eqs. (3) and (4), the ratios of which were
15:4, 5:3, and 1:1, for 50a, 50b, and 60a, respectively. Since the
chemical shifts of the signals observed for the syn and anti forms
for 50a, 50b, and 60a are in good agreement with those of the spec-
tra for the complexes having the Cl counter anions 5 and 6, the
ratios of 5a/5b and 6a/6b in the reaction mixtures shown in
Scheme 2 could be determined from the NMR criteria (vide supra,
see also the Section 3).
l
(M = Ir (5a), Rh (6a)) and their trans-isomers (M = Ir (5b), Rh
(6b)) with respect to the disposition of two Cp* ligands. The
ratios 5a:5b and 6a:6b in the reaction mixtures determined by
the NMR spectra were ca. 5:2 and 7:5, respectively (vide infra).
The anion metathesis using KPF6 in CH2Cl2 afforded the mixture
of cis-[Cp*Ir(CO)( -TeTol)2IrCp*Cl][PF6] (50a) and its trans-isomer
l
(50b) in ca. 5:2 ratio (Scheme 2), both of which were obtained
as single crystals and characterized by the X-ray analysis using
the crystals separated manually.
For the Ir–Rh complex 6, the X-ray structure could be
determined for 6a, since the suitable single crystals were avail-
able only for 6a from the mixture of the products 6a and 6b.
Strangely, when this mixture was treated similarly with KPF6,
Cp*
Cl
[(Cp*MCl) (µ-Cl) ]
(0.5 equiv)
Cp* Cl
Cl
2
2
Cp*
Te
Ir
Te
M
M
Ir
Te
Tol
1
+
Te
Tol
Cp*
Tol
C
O
CH Cl , r.t.
Cl
2
2
C
O
Tol
5b: M = Ir
5a: M = Ir
6b: M = Rh
6a: M = Rh
Cp*
Cl
Cp* PF
6
PF
6
Cp*
Te
Te
KPF (excess)
Ir
6
M
Ir
Ir
Te
Tol
+
Te
Cp*
C
O
Tol
Cl
CH Cl , r.t.
2
2
C
O
Tol
Tol
5'a: M = Ir
6'a: M = Rh
5'b
Scheme 2.

140
T. Nakagawa et al. / Journal of Organometallic Chemistry 695 (2010) 137–144
Table 2
Selected interatomic distances (Å) and angles (°) in 50a, 50b, and 60a.
50a
(a) Distances
Irꢀ ꢀ ꢀIr*
Ir–Te
Ir–Cl
C(11)–O
3.964(1)
2.6346(8)
2.336(7)
1.15(2)
Ir–Te*
Ir–C(11)
2.6287(7)
1.83(2)
(b) Angles (°)
Te–Ir–Te*
Ir–Te–C(12)
Ir–C(11)–O
81.76(2)
104.4(3)
174(2)
Ir–Te–Ir*
92.88(2)
107.2(3)
Ir*–Te–C(12)
50b
(a) Distances
Ir(1)ꢀ ꢀ ꢀIr(2)
Ir(1)–Te
Ir(1)–C(7)
C(7)–O
3.9742(8)
2.6425(8)
1.85(2)
Ir(2)–Te
Ir(2)–Cl
2.6409(8)
2.429(4)
1.14(2)
(b) Angles (°)
Te–Ir(1)–Te*
Ir(1)–Te–Ir(2)
Ir(2)–Te–C(8)
Fig. 3. An ORTEP drawing of the cation of 50a at 50% probability level. All hydrogen
82.22(2)
97.56(2)
110.9(2)
Te–Ir(2)–Te*
Ir(1)–Te–C(8)
Ir(1)–C(7)–O
82.28(2)
105.2(2)
175(1)
atoms are omitted for clarity.
A half of this structure is crystallographically
independent, which includes the CO and Cl ligands disordered with the 50:50
occupancies.
60a
(a) Distances
Irꢀ ꢀ ꢀRh
3.9702(6)
2.6339(6)
2.6371(7)
1.861(7)
1.123(8)
Ir–Te(1)
Ir–Te(2)
Ir–C(11)
C(11)–O
Rh–Te(1)
Rh–Te(2)
Rh–Cl(1)
2.6301(8)
2.6244(8)
2.366(2)
(b) Angles (°)
Te(1)–Ir–Te(2)
Ir–Te(1)–Rh
Ir–Te(1)–C(12)
Ir–Te(2)–C(19)
Ir–C(11)–O
81.74(2)
97.91(2)
103.7(2)
105.9(2)
178.2(6)
Te(1)–Rh–Te(2)
Ir–Te(2)–Rh
Rh–Te(1)–C(12)
Rh–Te(2)–C(19)
82.05(2)
97.98(2)
110.7(2)
109.5(2)
Tol
Te
–
–
+
Cp*
+
[PF ]
[PF ]
6
Cp*
6
Cp*
Te
Cp*
Ir
M
Ir
Te
Tol
M
5'a, 6'a
+
Te
Tol
CDCl
Tol
C
O
3
Cl
C
O
Cl
5'a-syn: M = Ir
5'a-anti: M = Ir
6'a-syn: M = Rh
6'a-anti: M = Rh
Fig. 4. An ORTEP drawing of the cation of 50b at 50% probability level. All hydrogen
atoms are omitted for clarity. Crystallographic mirror plane is present including two
Ir centers as well as the CO and Cl ligands.
Tol
Cl
Te
–
Cl
+
[PF ]
6
–
Cp*
+
[PF ]
6
Cp*
Te
Ir
Ir
Ir
Ir
5'b
+
Te
Tol
Cp*
CDCl
Te
Tol
5'b-anti
3
Cp*
C
O
Tol
C
O
5'b-syn
ð3Þ
Tol
Te
–
Cl
+
[PF ]
6
–
Cp*
+
Cl
[PF ]
6
Cp*
Te
Ir
Ir
Ir
Ir
5'b
+
Te
Cp*
CDCl
Te
Tol
5'b-anti
3
Cp*
C
O
Tol
C
Tol
O
5'b-syn
ð4Þ
2.3. Reactions of 1 with Ru(II) complexes
Treatment of 1 with 0.25 equiv. of [(Cp*Ru)4(
l3-Cl)4] in CH2Cl2
at room temperature resulted in the formation of the mixture,
the NMR spectrum of which showed the presence of four isomers
Fig. 5. An ORTEP drawing of the cation of 6a at 50% probability level. All hydrogen
atoms are omitted for clarity.
as observed for the reactions of 1 with [(Cp*MCl)2(
l-Cl)2] (M = Ir,

T. Nakagawa et al. / Journal of Organometallic Chemistry 695 (2010) 137–144
141
Rh) described above. This presumably suggests that the reaction
proceeds analogously, affording the tellurolato-bridged dinuclear
Ir–Ru complexes with cis and trans forms that are convertible to
the syn and anti forms in solutions. However, the product from this
reaction was not isolable in a pure form to be subjected for full
characterization.
Interestingly, when 1 was allowed to react with 0.75 equiv. of
[(Cp*Ru)4(
l
3-Cl)4] in CH2Cl2 at room temperature, a tetranuclear
complex [Cp*IrCl{ -Te(g6-Tol)RuCp*}2RuCp* (CO)]Cl2 (7) was ob-
tained in moderate yield. Preparation of the single crystals was at-
l
tempted by converting 7 to [Cp*IrCl{ -Te(g6-Tol)RuCp*}2RuCp*
l
(CO)][PF6]2 (70) through the metathetical reaction with KPF6. How-
ever, due to the poor quality of the crystals, the X-ray analysis was
unable to be completed. Nevertheless, it disclosed the atom con-
nectivities in 70 (Scheme 3).
Complex 70 has a dinuclear core bridged by two TeTol ligands,
where the dispositions of two Cp* ligands and two Tol groups are
cis and syn, respectively. There are no bonding interactions be-
tween Ir and Ru centers. Two Tol planes are oriented parallel to
the Ir–Ru vector and the Cp*Ru fragment binds to each of the ben-
zene rings of the
l-TeTol ligands, forming (p p-arene)
-Cp*)Ru(
chromophore. The 1H NMR spectrum of 7 is consistent with this so-
lid state structure. Characteristic high-field shifts of the resonances
due to the aryl protons of Tol groups in the 1H NMR spectrum
Fig. 6. An ORTEP drawing of the cation of 8 at 50% probability level. All hydrogen
atoms are omitted for clarity.
(d = 5.4–5.9) are diagnostic of the p
-coordination to the Cp*Ru cen-
ter. Unfortunately, since the Ir and Ru sites are disordered with ca.
50:50 occupancies, the ligand bonded to each metal, viz., either Cl
or CO, could not be determined crystallographically. However, the
Table 3
Selected interatomic distances (Å) and angles (°) in 8.
(a) Distances
Ir–Ru
Ir–Te(1)
Ru–Te(1)
Ru–C(11)
m
(C„O) value of 1937 cmꢁ1 observed for 7, which is lower by 85–
2.9037(5)
2.6048(4)
2.6348(6)
1.898(6)
93 cmꢁ1 than those observed for the CO ligands bound to the Ir(III)
centers in 2–6, indicates presumably that the CO is bonded to the
Ru center in 70. In relation to this assignment, it is to be noted, for
example, that [CpRu(CO)(PPh3)(SC6F5)] [6] and [Cp*Ir(CO)(SPh)2]
Ir–Te(2)
Ru–Te(2)
C(11)–O
2.6147(4)
2.6512(5)
1.135(8)
(b) Angles (°)
Te(1)–Ir–Te(2)
Ir–Te(1)–Ru
Ir–Te(1)–C(12)
Ru–Te(1)–C(12)
Ru–C(11)–O
84.36(1)
67.31(1)
110.3(2)
104.9(2)
178.5(5)
Te(1)–Ru–Te(2)
Ir–Te(2)–Ru
Ir–Te(2)–C(19)
Ru–Te(2)–C(19)
83.07(2)
66.93(1)
107.8(2)
107.7(2)
[7] show m
(CO) bands at 1956 and 1994 cmꢁ1, respectively.
The reaction of 1 with an equimolar amount of the Ru(II) com-
plex [RuH(cod)(MeCN)3][BPh4] resulted in the formation of the
dinuclear complex [Cp*Ir(
l-H)(l-TeTol)2Ru(CO)(cod)][BPh4] (8) in
moderate yield (Eq. (5)). The X-ray diffraction study has disclosed
its structure in detail as shown in Fig. 6 and Table 3.
and 2.6145(4) Å slightly or considerably shorter than those in 2,
3, 50, and 60 without metal–metal bond (2.63–2.67 Å). For compar-
ison, the Ir–Te bond lengths for the TePh ligand bridging to the Ir–
[BPh ]
4
H
[RuH(cod)(MeCN) ][BPh ] (1 equiv)
3
4
Cp*
Ir
Ru
1
Ir bond in the clusters [Ir6(CO)14(l (l-
-TePh)]ꢁ and [Ir6(CO)13
Te
THF, r.t.
Te
C
Tol
O
TePh)2] are 2.60–2.63 Å [5]. Although the hydride was unable to
be located from the Fourier map, appearance of the singlet reso-
nance at d ꢁ14.3 in the 1H NMR spectrum unambiguously indi-
cated the existence of the hydride ligand. The dihedral angle
between two IrRuTe planes at 106.4° suggests that the hydride is
presumably bridging the Ir–Ru bond to give the triply bridged Ir–
Ru core. As in 7 and 70, migration of the CO ligand from Ir to Ru oc-
Tol
8
ð5Þ
Complex 8 has a bimetallic core bridged by two TeTol ligands,
where the geometry of two Tol groups is anti with one axial and
one equatorial orientations. The Irꢀ ꢀ ꢀRu distance at 2.9038(4) Å
indicates the presence of bonding interactions between two metal
curred also in 8. The
higher than that in 7.
m
(C„O) value of 1994 cmꢁ1 is significantly
centers. This resulted in the Ir–
l
-Te bond distances at 2.6051(4)
Cp*
Cl
Cp*
Cp*
2
[PF ]
Cp*
Te
6 2
[(Cp*RuCl) (µ -Cl) ]
Te
4
3
4
Ir
KPF
Ru
C
6
Ir
Ru
C
Te
(0.75 equiv)
CH Cl , r.t.
(excess)
Te
1
Cl
Cl
Cp*Ru
2
2
Cp*Ru
RuCp*
RuCp*
O
Me
O
Me
Me
Me
7
7'
Scheme 3.

142
T. Nakagawa et al. / Journal of Organometallic Chemistry 695 (2010) 137–144
single-crystal X-ray analysis was performed for both 50a and 50b.
The data below were obtained by using some crystals collected
manually. Complex 50a: IR (KBr): 2030 ( C„O) cmꢁ1. Anal. Calc.
3. Experimental
3.1. General
m
for C35H44OF6PClTe2Ir2: C, 32.31; H, 3.41. Found: C, 32.29; H,
1
3.41%. H NMR (CDCl3): d 1.88, 2.21 (s, 15H each, Cp*), 2.30 (s,
All manipulations were carried out under N2 using standard
Schlenk techniques. Solvents were dried by common methods
and distilled under N2 before use. Complexes 1 [3], [MCl2(cod)]
6H, C6H4Me), 6.98, 7.32 (d, J = 8.0 Hz, 4H each, C6H4) for 50a-syn;
d 1.58, 1.80 (s, 15H each, Cp*), 2.35, 2.43 (s, 3H each, C6H4Me),
7.02, 7.64 (d, J = 8.0 Hz, 2H each, C6H4; the resonances for the
remaining 4 protons were not assignable) for 50a-anti. The ratio
of 50a-syn and 50a-anti was 15:4. Complex 50b: IR (KBr): 2030
(M = Pd [8], Pt [9]), [(Cp*MCl)2(
[(Cp*Ru)4(
l-Cl)2] (M = Ir, Rh) [10],
l
3-Cl)4] [11], and [RuH(cod)(MeCN)3][BPh4] [12] were
prepared according to the literature methods, while KPF6 was ob-
tained commercially and used as received.
IR and NMR spectra were recorded on a JASCO FT/IR-420 and a
JEOL alpha-400 spectrometer, respectively. Elemental analyses
were done with a Perkin–Elmer 2400 series II CHN analyzer.
(m
C„O) cmꢁ1. Anal. Calc. for C35H44OF6PClTe2Ir2: C, 32.31; H, 3.41.
Found: C, 32.23; H, 3.40%. 1H NMR (CDCl3): d 1.60, 2.09 (s, 15H
each, Cp*), 2.46 (s, 6H, C6H4Me), 7.18, 7.70 (d, J = 8.0 Hz, 4H each,
C6H4) for 50b-syn; d 1.63, 1.86 (s, 15H each, Cp*), 2.21, 2.37 (s, 3H
each, C6H4Me), 7.05, 7.11, 7.48, 7.54 (d, J = 8.0 Hz, 2H each, C6H4)
for 50b-anti. The ratio of 50b-syn and 50b-anti was 5:3.
3.2. Preparation of 2
3.5. Preparation of 6 and 60
A THF solution (5 cm3) containing 1 (40 mg, 0.050 mmol) and
[PdCl2(cod)] (15 mg, 0.050 mmol) was stirred at room tempera-
ture. The mixture changed immediately to an yellow suspension,
which was filtered off and the remained solid was extracted with
DMF. Addition of ether to the concentrated extract afforded yellow
Complex 6 was obtained as spectroscopically pure, dark red
powder from
1 l-Cl)2]
(79 mg, 0.10 mmol) and [(Cp*RhCl)2(
(31 mg, 0.050 mmol) by the analogous procedure to prepare 5
(81 mg, 73% yield). The NMR spectrum of the reaction mixture
showed the presence of 6a and 6b in the ratio of 7:5. Single crystals
of 6aꢀ0.2CH2Cl2ꢀ0.4C6H14 for the X-ray analysis were obtained from
CH2Cl2–hexane.
crystals of 2 (32 mg, 66% yield). IR (KBr): 2023 (m .
C„O) cmꢁ1 1H
NMR (DMSO-d6): d 2.20 (s, 15H, Cp*), 2.27 (s, 6H, C6H4Me), 7.05,
7.92 (d, J = 8.4 Hz, 4H each, C6H4). Anal. Calc. for C25H29OCl2Pd-
Te2Ir: C, 30.95; H, 3.01. Found: C, 31, 17; H, 3.09%.
Complex 6 (102 mg, 0.0926 mmol) was similarly converted to 60
upon treatment with KPF6 (35 mg, 0.19 mmol), which was ob-
tained as dark red needles of 60ꢀCH2Cl2 (84 mg, 75% yield based
on 6). The NMR spectrum of the reaction mixture disclosed the
3.3. Preparation of 3 and 4
After stirring the mixture of
1 (16 mg, 0.020 mmol) and
presence of only 60a. Complex 60aꢀCH2Cl2: IR (KBr): 2029 (mC„O
)
[PtCl2(cod)] (7.5 mg, 0.020 mmol) in THF (5 cm3) at room temper-
ature, the suspension was obtained immediately, which was fil-
tered off. The 1H NMR spectrum of the remained solid showed
the presence of two products, 3 and 4, in a molar ratio 3:5. Crystal-
lization of this solid using DMF–ether afforded only 4 as analyti-
cally pure, yellow crystals (11 mg, 59% yield based on Ir). The
results of the preliminary X-ray analysis disclosed the atom-con-
cmꢁ1. Anal. Calc. for C36H46OF6PCl3RhTe2Ir: C, 33.35; H, 3.58.
Found: C, 33.38; H, 3.59%. 1H NMR (CDCl3): d 1.81, 2.20 (s, 15H
each, Cp*), 2.32 (s, 6H, C6H4Me), 7.00, 7.44 (d, J = 8.0 Hz, 4H each,
C6H4) for 60a-syn; d 1.55, 1.85 (s, 15H each, Cp*), 2.36, 2.43 (s, 3H
each, C6H4Me), 7.02, 7.73 (d, J = 8.0 Hz, 2H each, C6H4; the reso-
nances for the remaining 4 protons were not assignable) for 60a-
anti. The ratio of 60a-syn and 60a-anti was 1:1.
necting scheme in 4. Complex 4: IR (KBr): 2022 (m .
C„O) cmꢁ1 1H
NMR (DMSO-d6): d 2.07 (s, 30H, Cp*), 2.34 (s, 12H, C6H4Me), 7.11,
7.75 (d, J = 8.0 Hz, 8H each, C6H4). Anal. Calc. for C50H58O2Cl2-
Te4Ir2Pt: C, 32.43; H, 3.15. Found: C, 32.11; H, 3.13%. Complex 3
was obtained by recrystallizing the evaporated residue of the
mother liquor from CH2Cl2–hexane but in the impure form and
could not be isolated in the analytically pure state despite the re-
peated crystallization. The structure of 3 was confirmed by using
the single crystals of 3ꢀC2H4Cl2 deposited in a small amount upon
crystallization from C2H4Cl2–ether. Complex 3: IR (KBr): 2022
3.6. Preparation of 7 and 70
A mixture of 1 (80 mg, 0.10 mmol) and [(Cp*RuCl)4(
l3-Cl)4]
(80 mg, 0.075 mmol) in CH2Cl2 (5 cm3) was stirred at room tem-
perature for 25 h. The resultant dark red solution was evaporated
to dryness in vacuo and the residue was crystallized from
ClCH2CH2Cl and hexane, affording 7 as dark red crystals (95 mg,
58% yield). IR (KBr): 1937 (m .
C„O) cmꢁ1 1H NMR (CDCl3): d 1.91,
2.02 (s, 15H each, Cp*), 1.99 (s, 30H, Cp*Ru), 2.12 (s, 6H, C6H4Me),
5.47–5.49 (br, 4H, C6H4), 5.52, 5.83 (d, J = 6.0 Hz, 2H each, C6H4).
In spite of the attempts to analytically pure 7, satisfactory C and
H analysis data were not obtained.
(m .
C„O) cmꢁ1 1H NMR (DMSO-d6): d 2.18 (s, 15H, Cp*), 2.30 (s, 6H,
C6H4Me), 7.06, 7.89 (d, J = 8.0 Hz, 4H each, C6H4).
3.4. Preparation of 5 and 50
Single crystals of 70 for the preliminary X-ray diffraction study
were obtained by treating 7 with 3 equiv. of KPF6 in CH2Cl2, fol-
lowed by crystallization of the product from C2H4Cl2–ether.
To a solution of 1 (918 mg, 1.15 mmol) in CH2Cl2 (30 cm3) was
added [(Cp*IrCl)2(
l-Cl)2] (465 mg, 0.584 mmol) at room tempera-
ture. After stirring for 20 h, the resultant solution was concentrated
in vacuo. Addition of hexane afforded spectroscopically pure 5 as
orange powder (1.39 g, 92% yield). The NMR spectrum of the reac-
tion mixture showed the presence of 5a and 5b in the ratio of 9:4.
A mixture of 5 (357 mg, 0.300 mmol) and KPF6 (106 mg,
0.576 mmol) in CH2Cl2 (5 cm3) was stirred at room temperature
for 2 h and the resultant mixture was filtered. Addition of hexane
to the concentrated filtrate gave 50 as a mixture of 50a as platelike
crystals and 50b as prismatic crystals in the combined yield of
316 mg (80% based on 5). The NMR spectrum of the reaction mix-
ture indicated the formations of 50a and 50b in the ratio of 5:2. The
3.7. Preparation of 8
To a solution of 1 (75 mg, 0.095 mmol) in THF (5 cm3) was
added [RuH(cod)(MeCN)3][BPh4] (62 mg, 0.095 mmol) and the
mixture was stirred at room temperature for 4 h. Addition of ether
to the concentrated product solution gave 8 as dark red crystals
(53 mg, 42% yield). IR (KBr): 1994 (
m .
C„O) cmꢁ1 1H NMR (CDCl3):
d ꢁ14.3 (s, 1H,
l
-H), 1.91, 2.23 (s, 15H, Cp*), 2.27, 2.38 (s, 3H each,
C6H4Me), 2.0–2.6 (6H, CH2 of cod), 2.67 (br, 2H, CH2 of cod), 3.51,
3.61, 3.83, 4.50 (br, 1H each, CH of cod), 6.87, 6.89 (d, J = 8.0 Hz,
2H each, C6H4), 7.00–7.05 (4H, C6H4), 6.88 (t, J = 7.2 Hz, 4H, p-H

T. Nakagawa et al. / Journal of Organometallic Chemistry 695 (2010) 137–144
143
Table 4
Crystal data for 2, 3ꢀC2H4Cl2, 50a-syn, 50b-syn, 6a-synꢀC6H14, and 8.
2
3ꢀC2H4Cl2
50a-syn
50b-syn
6a-
8
synꢀ0.2CH2Cl2ꢀ0.4C6H14
Formula
Formula weight
Space group
a (Å)
b (Å)
c (Å)
C25H29OCl2PdTe2Ir C27H33OCl6Te2IrPt C35H44OF6PClTe2Ir2 C35H44OF6PClTe2Ir2 C37.6H50OCl2.4RhTe2Ir
C57H62BORuTe2Ir
1322.42
970.23
1228.79
P21/m (No. 11)
9.774(2)
15.266(3)
10.844(2)
95.398(1)
1610.8(6)
2
1300.79
P21212 (No. 18)
14.103(4)
15.882(4)
9.082(3)
90
1300.79
I4/m (No. 87)
21.208(1)
21.208(1)
17.809(1)
90
1153.42
P212121 (No. 19)
8.857(2)
15.095(3)
31.425(7)
90
P21/n (No. 14)
10.196(1)
22.581(3)
12.606(2)
107.724(1)
2764.6(5)
4
P21/n (No. 14)
11.470 (2)
14.821(2)
29.624(5)
94.0274(5)
5023(1)
b (°)
V (Å3)
2022(1)
2
8010.0 (5)
8
4201(2)
4
Z
4
1.75
qcalcd (g cmꢁ3
)
2.33
2.53
2.14
2.16
1.82
Crystal size (mm3)
0.30 ꢂ 0.30 ꢂ 0.20 0.20 ꢂ 0.10 ꢂ 0.10 0.60 ꢂ 0.30 ꢂ 0.15
0.40 ꢂ 0.30 ꢂ 0.15
0.40 ꢂ 0.30 ꢂ 0.15
0.40 ꢂ 0.10 ꢂ 0.03
Number of unique reflections
Number of data observed
6283
5246
3811
2300
4632
3295
4744
9625
11469
2668
6662
8620
(I > 2r(I))
Number of variables
318
202
241
265
455
629
Transmission factor
0.121–0.212
0.029
0.096
0.028–0.341
0.034
0.103
0.105–0.294
0.042
0.123
0.094–0.290
0.054
0.169
0.283–0.465
0.031
0.061
0.583–0.883
0.042
0.123
a
R1
wR2
b
GOFc
1.02
1.02
1.02
1.03
1.04
1.02
a
b
c
R1
=
R
||Fo| ꢁ |Fc||/
R
|Fo| (I > 2
2
r
(I)).
P
P
2
1=2
wR2 ¼ ½ ðwðF2o ꢁ Fc2Þ Þ= wðF2oÞ ꢃ
GOF = [
(all data).
R
w(|Fo| ꢁ |Fc|)2/{(no. observed) ꢁ (no. variables)}]1/2
.
of BPh4), 7.03 (t, J = 7.2 Hz, 8H, m-H of BPh4), 7.42 (br, 8H, o-H of
BPh4). Anal. Calc. for C57H62OBRuTe2Ir: C, 51.77; H, 4.73. Found:
C, 51.69; H, 4.15% (Table 4).
tion through Cooperation of Science and Engineering” from the
Ministry of Education, Culture, Sports, Science and Technology, Ja-
pan. Grant-in-Aid for JSPS Fellows (20-6569) is also appreciated
(T.N.).
3.8. X-ray crystallography
Appendix A. Supplementary material
Single crystals of 2, 3ꢀ2C2H4Cl2, 50a-syn, 50b-syn, 6a-synꢀ0.2-
CH2Cl2ꢀ0.4C6H14, and 8 were sealed in glass capillaries under argon
and mounted on a Rigaku Mercury-CCD diffractometer equipped
CCDC 745322, 745323, 745324, 745325, 745326 and 745327
contain the supplementary crystallographic data for 50b-syn, 50a-
syn, 6a-syn, 2, 8 and 3. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associ-
ated with this article can be found, in the online version, at
doi:10.1016/j.jorganchem.2009.09.038.
with a graphite-monochromatized Mo Ka source. Diffraction stud-
ies for 2, 50a-syn, 50b-syn, and 8 were done at room temperature,
while those for 3ꢀ2C2H4Cl2 and 6a-synꢀ0.2CH2Cl2ꢀ0.4C6H14 were
at 113 K. Data collections were performed by using the CRYSTALCLEAR
program package [13]. All data were corrected for Lorentz and
polarization effects as well as absorption.
Structure solution and refinements were conducted by using
the CRYSTALSTRUCTURE program package [14]. The positions of non-
hydrogen atoms were determined by Patterson methods (PATTY)
[15] and subsequent Fourier synthesis (DIRDIF99) [16], which were
refined by full-matrix least-squares techniques using anisotropic
thermal parameters. Hydrogen atoms were placed at the calculated
positions and included at the final stages of the refinements with
fixed parameters.
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Fw = 1851.84; space group, P21/n (no. 14); a = 10.555(9),
b = 15.73(1), c = 17.98(2) Å, b = 96.051(4)°, V = 2967(4) Å3; Z = 2;
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q
calc = 2.07 g cmꢁ3; crystal size, 0.40 ꢂ 0.10 ꢂ 0.10 mm3; no of un-
ique reflections, 5958; no of variables, 176; R1 value using the data
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70ꢀC2H4Cl2: formula, C56H78Cl3F12IrOP2Ru3Te2; Fw = 1914.15; space
group, P21/c (no. 14); a = 13.296(4), b = 14.500(4), c = 34.04(1) Å,
b = 93.831(2)°, V = 6547(3) Å3; Z = 4;
q
calc = 1.94 g cmꢁ3; crystal
size, 0.20 ꢂ 0.20 ꢂ 0.20 mm3; no of unique reflections, 14 505; no
of variables, 545; R1 value using the data of I > 2r(I), 0.070; wR2 va-
lue using all data, 0.21; GOF, 1.01.
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[12] T.V. Ashworth, R.H. Reimann, E. Singleton, J. Chem. Soc., Dalton Trans. (1978)
1036.
Acknowledgements
[13] CRYSTALCLEAR 1.3.6: Rigaku/MSC: 9009 New Trails Dr., The Woodlands, TX 77381,
USA, 1998–2006.
[14] CRYSTALSTRUCTURE 3.8.0: Crystal structure analysis package, Rigaku and Rigaku/
MSC: 9009 New Trails Dr., The Woodlands, TX 77381, USA, 2000–2006.;
This work was supported by Grant-in-Aid for Scientific Re-
search on Priority Areas (No. 18065005, ‘‘Chemistry of Concerto
Catalysis”) and in part by Global COE Program ‘‘Chemistry Innova-

144
T. Nakagawa et al. / Journal of Organometallic Chemistry 695 (2010) 137–144
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