Stepwise formation of quasi-octahedral macrocyclic complexes of rhodium(III) and iridium(III) bearing a pentamethylcyclopentadienyl group

Article abstract of DOI:10.1002/1521-3765(20020118)8:2<372::AID-CHEM372>3.0.CO;2-L

Reactions of [{MCl₂(Cp*)}₂] (1: M=Ir, 2: M=Rh) with bidentate ligands (L) such as 1,4-diisocyano-2,5-dimethylbenzene (a), 1,4-diisocyano-2,3,5,6-tetramethylbenzene (b), pyrazine (c) or 4,4′-dipyridyl (d) gave the corresponding dinuclear complexes [{MCl₂(Cp*)}₂(L)] (M=Ir: 3a, 3b, 5c, 5d; M=Rh: 4b, 6c, 6d), which were converted into tetranuclear complexes [{M₂ (μ-Cl)₂(Cp*)₂} ₂(L)₂](OTf)₄ (M=Ir: 7c, 7d, 9a, 9b; M=Rh: 8c, 8d, 10b) on treatment with Ag(OTf). X-ray analyses of 8c and 8d revealed that each of four pentamethylcyclopentadienyl metal moieties was connected by two μ-Cl-bridged atoms and a bidentate ligand to construct a rectangular cavity with the dimensions of 3.7 × 7.0 A for 8c and 3.7 × 11.5 A for 8d. Both the Rh₂Cl₂ and pyrazine (or 4,4′dipyridyl) ring planes are perpendicular to the Rh₄ plane. Treatment of Cl-bridged complexes (7c, 7d, 8c, 8d, 9b, and 10b) with a different ligand (L') resulted in cleavage of the Cl bridges to produce two-dimensional complexes [{MCI(Cp*)}₄{(L)-(L')}₂](OTf)₄ (11ac, 11bc, 11bd, 12bc, and 12bd) with two different ligand edges . Complex 10b reacted readily with 1,4-diisocyano-2,3,5,6-tetramethyl-benzene (b) to give a tetranuclear rhodium(III) complex 12bb. The structure of tetranuclear complexes was confirmed by X-ray analysis of 11bc. Each {(MCp*} moiety is surrounded by a Cl atom, isocyanide, and pyrazine (or 4,4′-dipyridyl) and the dimensions of its cavity are 7.0 × 11.6 A.

Full text of DOI:10.1002/1521-3765(20020118)8:2<372::AID-CHEM372>3.0.CO;2-L

FULL PAPER
Stepwise Formation of Quasi-Octahedral Macrocyclic Complexes of
Rhodium(iii) and Iridium(iii) Bearinga Pentamethylcyclopentadienyl Group
Yasuhiro Yamamotoa,*[a] Hajime Suzuki,[a] Nobuo Tajima,[b] and Kazuyuki Tatsumi[b]
Abstract: Reactions of [{MCl2(Cp*)}2]
(1: M ˆ Ir, 2: M ˆ Rh) with bidentate
ligands (L) such as 1,4-diisocyano-2,5-
dimethylbenzene (a), 1,4-diisocyano-
2,3,5,6-tetramethylbenzene (b), pyra-
zine (c) or 4,4'-dipyridyl (d) gave the
corresponding dinuclear complexes
[{MCl2(Cp*)}2(L)] (M ˆ Ir: 3a, 3b, 5c,
5d; M ˆ Rh: 4b, 6c, 6d), which were
converted into tetranuclear complexes
[{M2(m-Cl)2(Cp*)2}2(L)2](OTf)4 (M ˆ Ir:
7c, 7d, 9a, 9b; M ˆ Rh: 8c, 8d, 10b) on
treatment with Ag(OTf). X-ray analyses
of 8c and 8d revealed that each of
four pentamethylcyclopentadienyl met-
al moieties was connected by two m-Cl-
bridged atoms and a bidentate ligand to
construct a rectangular cavity with the
dimensions of 3.7 Â 7.0 ä for 8c and
3.7 Â 11.5 ä for 8d. Both the Rh2Cl2 and
pyrazine (or 4,4'dipyridyl) ring planes
are perpendicular to the Rh4 plane.
Treatment of Cl-bridged complexes
(7c, 7d, 8c, 8d, 9b, and 10b) with a
different ligand (L') resulted in cleavage
of the Cl bridges to produce two-dimen-
sional complexes [{MCl(Cp*)}4{(L)-
(L')}2](OTf)4 (11ac, 11bc, 11bd, 12bc,
and 12bd) with two different ligand
™edges∫. Complex 10b reacted readily
with 1,4-diisocyano-2,3,5,6-tetramethyl-
benzene (b) to give a tetranuclear rho-
dium(iii) complex 12bb. The structure of
tetranuclear complexes was confirmed
by X-ray analysis of 11bc. Each {MCp*}
moiety is surrounded by a Cl atom,
isocyanide, and pyrazine (or 4,4'-dipyr-
idyl) and the dimensions of its cavity are
7.0 Â 11.6 ä.
Keywords: cyclopentadienyl ligands
¥
iridium,
¥ isocyanide ligands ¥
rhodium ¥ supramolecular chemistry
clopentadienyl groups, and their derivatives, since a new type
of supramolecular series would be developed by introduction
of these organic moieties. Since these six- or five-membered
rings block three sites on the octahedron, they reduce the
dimensionality of the polymeric derivatives and render them
paticularly amendable to processing. Octahedral building
blocks can be assemabled to form cubic or ladder-shaped
structures. Introduction of three-coordinate ring ligands also
can enhance solubility of polymeric compounds. We report
here stepwise assembly of the tetranuclear rhodium and
iridium supramolecules bearing pentamethylcyclopentadienyl
and binary ligands. Complexes reported here are novel
because they contain two-dimensional architectures with
two different ligand ™edges∫, that is, molecular rectangles.
The only self-assembled supramolecules with pentamethylcy-
clopentadienyl or cyclopentadienyl groups, to our knowledge,
have been reported by Rauchfuss et al.:[8, 9] [Co4Rh4(CN)12-
(Cp)4(Cp*)4]4‡, [Rh7(Cp*)7(CN)12]2‡, and [Ir4Rh3(CN)12-
(Cp*)7]2‡ (Cp* ˆ C5Me5). They are cyanide-linked molecular
squares and cubes that contain octahedral building blocks of
rhodium and cobolt derivatives. Recently Darensbourg et al.
reported the preparation of diamond-shaped heterometallic
complexes of cyclopentadienyl iron(ii) and copper(i) bridged
by cyanide groups.[10]
Introduction
Metal-containing supramolecules and coordination polymers
have attracted interests in recent years because there are
many promising metal fragments available for the construc-
tion of novel supramolecular materials.[1] In particular,
square-planar complexes of platinum and palladium are
attractive as building blocks which occupy vertices. For
example, diphosphines and diamine derivatives as ligands in
metallic building blocks have been used widespread by many
groups.[2] The sixfold bridging capability of the octahedral unit
leads to compounds with diverse dimensionality, in compar-
ison with those that are square planar.[3 7] We were interested
in supramolecular complexes based on quasi-octahedral geom-
etries that bear arene, cyclopentadienyl, or pentamethylcy-
[a] Prof. Y. Yamamotoa, H. Suzuki
Department of Chemistry, Faculty of Science
Toho University, Miyama, Funabashi, Chiba 274-8510 (Japan)
Fax : (‡81)47-475-1855
E-mail: yamamoto@chem.sci.toho-u.ac.jp
[b] N. Tajima, Prof. K. Tatsumi
Research Center for Materials Science and Department of Chemistry
Graduate School of science, Nagoya University, Furo-cho
Chikusa-ku, Nagoya 454-8602 (Japan)
A preliminary account of our work has been pub-
lished.[11]
Fax : (‡81)52-789-2943
E-mail: i45100a@nucc.cc.nagoya-u.ac.jp
372
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Chem. Eur. J. 2002, 8, No. 2

372 379
centers are connected by a m-diisocyanide ligand. X-ray
crystal analysis of 3a confirmed the structure (Figure 1
below). The rhodium analogue 4b, [{RhCl2(Cp*)}2{m-1,4-
(NC)2-2,3,5,6-Me4C6}], was prepared as orange crystals in
high yield by the reaction of [{RhCl2(Cp*)}2] (2) with b
(Scheme 1).
Results and Discussion
Di- and tetranuclear complexes: When bis[dichloro(penta-
methylcyclopentadienyl)iridium(iii)] (1) was treated with 1,4-
diisocyano-2,5-dimethylbenzene (a) or 1,4-diisocyano-2,3,5,6-
tetramethylbenzene (b) in a 1:1 molar ratio at room temper-
ature, yellow crystals formulated as [{IrCl2(Cp*)}2(CN-R-
NC)] (3a: R ˆ 2,5-Me2C6H2; 3b: R ˆ 2,3,5,6-Me4C6) by FAB
mass spectroscopy, were formed in high yields (Scheme 1).
The IR spectra showed a strong band at approximately
2140 cmÀ1 due to a terminal isocyanide group. In the 1H NMR
spectra two singlet resonances due to the Cp* and Me protons
appeared at about d ˆ 1.86 and 2.40, respectively. These
spectroscopic data indicate a dimeric structure in which the Ir
Treatment of 1 or 2 with pyrazine (c) also generated the
dinuclear complexes, 5c (M ˆ Ir) and 6c (M ˆ Rh)
[{MCl2(Cp*)}2(m-C4H4N2)]. In the 1H NMR spectra in
[D6]DMSO, two singlets appeared at about d ˆ 1.62 and
8.65, due to Cp* and pyrazine protons, respectively. Analo-
gously, the reactions with 4,4'-dipyridyl (d) gave dinuclear
complexes , [{MCl2(Cp*)}2(m-4,4'-dipyridyl)] 5d (M ˆ Ir) and
1
6d (M ˆ Rh). The H NMR spectra in [D6]DMSO showed
[{MCl2(Cp*)}2]
1: M=Ir
2: M=Rh
CN-R-NC
pyrazine
bipyridyl
R1
R2
R2
N
N
M
M
M N
Cl
N
M
M
CN
NC
M
Cl
Cl
Cl
Cl
Cl
Cl
R1
Cl
Cl
5c: M=Ir
Cl
Cl
Cl
5c: M=Ir
6c: M=Rh
3: M=Ir (a: R1=Me, R2=H: b: R1=R2=Me)
4: M=Rh (a: R1=Me, R2=H; b: R1=R2=Me)
6c: M=Rh
Ag(OTf)
Ag(OTf)
Ag(OTf)
4,4'-bipyridyl
Ag(OTf)
4+
pyrazine
Ag(OTf)
Cl
4+
4+
Cl
M
Cl
Cl
M
M
M
Cl
M
N
M
N
N
N
Cl
R2
R1
C
N
C
N
R1
R2
R1
R2
R2
R1
N
N
N
N
Cl
Cl
N
C
N
C
Cl
M
M
M
M
Cl
Cl
M
pyrazine
M
7c: M=Ir
7d: M=Ir
Cl
8c: M=Rh
8d: M=Rh
4,4'-bipyridyl
9a: M=Ir (R1=Me, R2=H);
9b: M=Ir (R1=R2=Me)
10b: M=Rh (R1=R2=Me)
CN-R-NC
R1 R2
R2
4+
R1
4+
M
N
CN
R2
NC
R1
M
M
N
M
N
CN
NC
CN-R-NC
Cl
Cl
Cl
Cl
Cl
R2 R1
N
R1 R2
CN
4+
R2
N
R1
N
Cl
N
M
NC
M
N
R2
M
CN
NC M
R1
CN
R2
R1
Cl
Cl
R2
Cl
Cl
C
N
R2
R1
C
N
M
NC
R1
M
R1
R2
R2
R2
R1
R1
R2
11ac: M=Ir (R1=Me, R2=H)
11bc: M=Ir (R1=R2=Me)
12bc: M=Rh (R1=R2=Me)
R1
N
C
N
C
11bd: M=Ir (R1=R2=Me)
12bd: M=Rh (R1=R2=Me
R2
R1
R2
Cl
Cl
M
NC
R1
CN
M
12bb: M=Rh (R1=R2=Me)
Scheme 1.
Chem. Eur. J. 2002, 8, No. 2
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373

Y. Yamamotoa et al.
FULL PAPER
three resonances at approximately d ˆ 1.60 (s), 7.80 (d) and
8.70 (d); the fisrt is assigned to the Cp* protons, and the others
are assigned to dipyridyl protons.
correspond to the [M]4‡ and [M À 2pyrazine]4‡ charge state
species, respectively, where M is a cationic species. The masses
of the 4 ‡ ion were determined to be 1981.6 and 1821.2, which
are in nearly agreement with the theoretical masses of 1980.23
and 1820.05, respectively. In the IR spectrum, the CN band
appeared at 2176 cmÀ1. The 1H NMR spectrum showed three
singlets at d ˆ 1.94, 2.42, and 8.65 in a 30:12:4 intensity ratio,
due to Cp*, isocyanide, and pyrazine protons, respectively.
Finally, the structure was determined by X-ray analysis
(Figure 4 later). The complex has a tetranuclear rectanglar
structure, and each iridium atom is surrounded by an
isocyanide, a pyrazine, a Cl atom, and a Cp* moiety.
Tetranuclear complex 11ac, [{IrCl(Cp*)}4(m-pyrazine)2{m-1,4-
(NC)2-2,5-Me2C6H2}2](OTf)4, which bears the 1,4-diisocyano-
2,5-dimethylbenzene (a) and pyrazine (c) ligands, was pre-
pared by a direct reaction of 3a with pyrazine in the presence
of Ag(OTf) (Scheme 1). The rhodium analogue 12bc was
obtained in 49% yield from a direct reaction of 4b with
pyrazine in the presence of Ag(OTf). Tetranuclear iridium
and rhodium complexes 11bd and 12bd bearing isocyanide
and 4,4'-dipyridyl ligands were prepared by the direct treat-
ment of 3b or 4b with 4,4'-dipyridyl (d). Complex 10b reacted
readily with b to give the rectangular complex 12bb in which
the four sides were sourrounded by isocyanide ligands. The IR
spectrum showed a terminal isocyanide at 2186 cmÀ1. The
1H NMR spectrum showed two singlets at d ˆ 1.85 and 1.87
due to Cp* protons and a broad resonance at d ˆ 2.39 due to
methyl protons, which suggests the presence of isomers.
When dinuclear complex 6c was treated with AgOTf (Tf ˆ
CF3SO2) in a 1:2 molar ratio in a mixture of CH2Cl2 and
MeCN at room temperature, tetranuclear complex 8c,
formulated as [{RhCl(Cp*)}4(m-pyrazine)2](OTf)4 from the
‡
FAB mass spectroscopy (m/z 1254 ([M‡1] ) and elemental
analysis, was formed (Scheme 1). The 1H NMR spectrum
consists of two characteristic singlets at d ˆ 1.61 and 8.65 in a
60:8 intensity ratio, suggesting a symmetric tetranuclear
structure. A tetranuclear iridium complex 7c was obtained
from 5c and AgOTf in a manner similar to the rhodium
analogue. The 1H NMR spectrum showed two kinds of
resonances for each of the Cp* and pyrazine ligands; at d ˆ
1.58 and 1.74 for the former and at d ˆ 8.84 and 8.97 for the
latter, suggesting the presence of configurational isomers.
Tetranuclear complexes that bear the 4,4'-dipyridyl ligand,
[{M(m-Cl)(Cp*)}4(m-bipyridyl)2](OTf)4 (7d: M ˆ Ir; 8d: M ˆ
Rh), were obtained by the reactions between the correspond-
1
ing neutral dinuclear complexes and Ag(OTf). The H NMR
spectra for 7d showed a singlet at d ˆ 1.60 due to Cp* protons
and a complex resonance at about d ˆ 8.5 due to dipyridyl
protons; that for 8d had two kinds of singlets at d ˆ 1.59 and
1.61 due to Cp* protons and a complex resonance at about
d ˆ 8.5 due to dipyridyl protons. The spectra of complex 8d
indicated the presence of configurational isomers, as did that
in the case of 7c. Detailed structures were confirmed by X-ray
analyses of 8c and 8d (Figures 2 and 3 later). They revealed
that the complex cations have the rectangular structures
bridged by four Cl atoms, and two pyrazine or 4,4'-dipyridyl
molecules.
The dinuclear isocyanide complexes 3b and 4b reacted
readily with Ag(OTf) to give complexes formulated as [{M(m-
Cl)(Cp*)}4(m-1,4-(NC)2-2,3,5,6-Me4C6)2](OTf)4, 9b (M ˆ Ir)
and 10b (M ˆ Rh) (Scheme 1). The IR spectra of 9b and
10b showed a terminal isocyanide bands at 2186 and
2182 cmÀ1, respectively. The 1H NMR spectra showed two
sharp singlets at d ˆ 1.94 and 2.42 for 9b and at d ˆ 1.85 and
2.37 for 10b, due to Cp* and methyl protons of the isocyanide
ligand, respectively. Based on the spectroscopy and structures
of pyrazine and 4,4'-dipyridyl complexes 9b and 10b were
assumed to be a structure bridged by four Cl atoms and two
isocyanide ligands.
Reactions of 8c with Lewis bases and of 3c with K[Ag(CN)2]:
Reaction of 8c with four equivalents of mesityl isocyanide at
room temperature replaced pyrazine ligands and Cl atoms to
give [RhCl(Cp*)(MesNC)2](OTf) together with recovery of
the starting compound 8c. A similar reaction with bis(diphe-
nylphosphino)ethane (dppe) gave [RhCl(Cp*)(dppe)](OTf).
These reactions arised from strong coordination ability of
dppe and isocyanide (Scheme 2). In an attempt to prepare a
complex bearing a silver atom, the reaction of 3a with
K[Ag(CN)2] was carried out and led to the replacement of two
Cl anions with CN anions to give yellow crysyals formulated
as [{IrCl(CN)(Cp*)}2{m-1,4-(CN)2-2,3,5,6-Me4C6}] from the
FAB mass spectroscopy and elemental analysis. The IR
spectrum showed two NC stretching frequencies at 2170 and
2128 cmÀ1. The 1H NMR spectrum showed two characteristic
When m-chloro-bridged complex
7c was treated with two equivalents
of b, the Cl bridges were replaced
+
by b to produce yellow crystals 11bc
formulated as [{IrCl(Cp*)}4(m-pyra-
2 dppe
4+
Cl
Cl
Rh
zine)2{m-1,4-(NC)2-2,3,5,6-Me4C6}2]-
Rh
Rh
PPh2
(OTf)4. This complex can be also
obtained by the reaction between
9b and pyrazine or the direct reac-
tion of 3b with pyrazine in the
presence of Ag(OTf) (Scheme 1).
The tetranuclear complex with a
4 ‡ charge was revealed by the ESI
technique. The isotopically resolved
signal centered at m/z 495 and 455
Cl
Ph2P
N
N
N
N
+
Cl
Cl
4 MesNC
Rh
Rh
Cl
CNR
Rh
RNC
Scheme 2.
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Rh and Ir Macrocyclic Complexes
372 379
resonances at d ˆ 1.98 and 2.41, assignable to Cp* and methyl
protons, respectively. The spectroscopic data suggest a
symmetric structure in which each iridium center was
surrounded by Cp*, Cl, CN, and isocyanide ligands.
Molecular structures: Detailed discussion of distances and
angles is avoided here because of the low accuracy of the
X-ray data, especially the methyl groups on the Cp* rings, for
the complexes 3a, 8c, 8d, and 11bc, but the tables of selected
bond lengths and angles are given.
Crystal structure of 3a: A perspective drawing of 3a with the
atomic numbering scheme is given in Figure 1 and selected
bond lengths and angles are listed in Table 1. The crystal unit
has a crystallographically imposed inversion center in the
middle of the Ir¥¥¥ Ir vector. The molecule has a dimeric
structure connected by a m-diisocyanide ligand, and the
iridium atoms are surrounded by two Cl atoms and isocyanide.
Angles between adjacent atoms around the iridium atoms are
nearly 908. The two Ir atoms are separated by 11.6 ä. The Ir1-
C11-N1 and C11-N1-C12 angles are 176 and 1728, respective-
ly, and compare well with those for other isocyanide
complexes.
Figure 2. Complex cation of [{Rh(m-Cl)(Cp*)}4(m-pyrazine)2](CF3SO3)4 ¥
2MeOH (8c ¥ 2MeOH).
consist of a cavity with the dimensions of 11.44 Â 7.21 ä.[12]
These values are closely similar to that of the corresponding
À
À
dimention for 8c or 8d. The Rh1 Rh1* and Rh2 Rh2*
diagonal lengths in the rectangular structure are approxi-
mately 7.9 and 12.0 ä for 8c and 8d, respectively. The bridged
Cl1 ¥¥¥ Cl2 separation is 3.28 ä. The dihedral angles between
the Rh1-Rh2-Cl1-Cl2 plane and pyrazine (4,4'-dipyridyl)
ligands are 90.9 and 92.28 for 8c and 90.58 and 91.48 for 8d,
respectively. The dihedral angles between two pyridine rings
of the dipyridyl ligand for 8d is 5.88, compared with that of
1.48 between two pyrazine ligands for 8c. The stacking
Figure 1. Molecular structure of [{IrCl2(Cp*)}2(m-1,4-(NC)2-2,5-Me2C6H2)]
(3a).
Crystal structures of 8c and 8d: Perspective drawings of 8c ¥
2MeOH and 8d with the atomic numbering schemes are
given in Figures 2 and 3, respectively, and selected bond
lengths and angles are listed in Tables 2 and 3. The crystal
units of 8c and 8d also consist of the molecule with a
crystallographically imposed inversion center in the middle of
the Rh1 ¥¥¥ Rh1* or Rh2 ¥¥¥ Rh2*, respectively, vector similar
to the structure of 3a. Methanol is contained as a solvent
molecule in the crystal unit of 8c (but outside of the square
framework). The complex cations have a rectangular cavity
bridged by four Cl atoms and two pyrazine or 4,4'-dipyridyl
molecules with the dimensions of 3.68 Â 7.02 ä for 8c, and of
3.68 Â 11.45 ä for 8d, respectively. The molecular rectangle of
[{ReBr(CO)3}4(m-pyrazine)2(m-4,4'-dipyridyl)2] is known to
Table 1. Selected bond lengths [ä] and angles [8] for compound 3a.
À
À
Ir1 Cl1
2.393(4)
1.96(1)
Ir1 Cl2
2.411(4)
1.13(2)
À
À
Ir1 C11
C11 N1
Cl1-Ir1-Cl2
Cl2-Ir1-C11
C11-N1-C12
88.9(2)
87.7(5)
172(1)
Cl1-Ir1-C11
Ir1-C11-N1
92.1(4)
176(1)
intramolecular interacts
Ir1 ¥¥¥ Ir1*
Figure 3. Complex cation of [{Rh(m-Cl)(Cp*)}4(m-4,4'-bipyridyl)2](CF3-
SO3)4 (8d).
11.6
Chem. Eur. J. 2002, 8, No. 2
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Y. Yamamotoa et al.
FULL PAPER
Table 2. Selected bond lengths [ä] and angles [8] for compound 8c.
Table 4. Selected bond lengths [ä] and angles [8] for 11bc.
À
À
À
À
Rh1 Cl1
2.466(3)
2.133(7)
2.459(2)
Rh1 Cl2
2.467(2)
2.474(3)
2.153(8)
Ir1 Cl1
2.379(5)
1.92(2)
2.368(5)
1.96(2)
2.408(5)
1.98
Ir1 N1
2.12(1)
1.18(2)
2.11(1)
1.14
2.11(1)
1.14(2)
2.12(1)
1.13(2)
À
À
À
À
Rh1 N1
Rh2 Cl2
Ir1 C12
C12 N4
À
À
À
À
Rh2 Cl2
Rh2 N2
Ir2 Cl2
Ir2 N2
À
À
Ir2 C5
C5 N3
Cl1-Rh1-Cl2
Cl2-Rh1-N1
Cl1-Rh2-N2
intramolecular interacts
Rh1 ¥¥¥ Rh2
83.50(8)
87.8(2)
88.5(2)
Cl1-Rh1-N1
Cl1-Rh2-Cl2
Cl2-Rh2-N2
88.0(2)
83.47(8)
88.5(2)
À
À
Ir3 Cl3
Ir3 N5
À
À
Ir3 C48
C48 N8
À
À
Ir4 Cl4
2.395(4)
1.98(2)
Ir4 N6
À
À
Ir4 41
C41 N7
3.68
7.02
Rh1 ¥¥¥ Rh2*
Cl1 ¥¥¥ Cl2
7.98
3.28
Rh1 ¥¥¥ Rh1*
Cl1-Ir1-N1
N1-Ir1-C12
Cl2-Ir2-C5
Cl3-Ir3-N5
N5-Ir3-C48
Cl4-Ir4-C41
87.5(4)
87.2(6)
87.7(5)
86.0(4)
90.5(6)
87.8(5)
Cl1-Ir1-C12
Cl2-Ir2-N2
N2-Ir2-C5
Cl3-Ir3-C48
Cl4-Ir4-N6
N6-Ir4-C41
86.7(6)
86.5(4)
90.8(6)
88.8(5)
86.0(4)
93.2)(6)
Table 3. Selected bond lengths [ä] and angles [8] for compound 8d.
À
À
Rh1 Cl1
2.4632(9)
2.134(3)
2.454(1)
Rh1 Cl2
2.447(1)
2.4760(9)
2.134(3)
À
À
Rh1 N1
Rh2 Cl1
intramolecular interactions
Ir¥¥¥ Ir 6.986(1), 7.0145(9);
À
À
Rh2 Cl2
Rh2 N2
11.6459(9), 11.668(1)
Cl1-Rh1-Cl2
Cl2-Rh1-N1
Cl1-Rh2-N2
83.64(3)
89.55(8)
89.49(8)
Cl1-Rh1-N1
Cl1-Rh2-Cl2
Cl2-Rh2-N2
88.31(8)
83.21(3)
89.10(9)
asymmetric unit of the crystal of 11bc consists of two halves
of the molecules, and each has crystallographically
a
imposed inversion center in the middle of the Ir¥¥¥ Ir* vector.
The complex has a tetranuclear rectangular structure with
Ir¥¥¥ Ir* lengths of 6.986(1) ä (7.0145(9) ä) and 11.6459(9) ä
(11.668(1) ä). Methanol is contained as a solvent molecule in
the cryatal unit similar to 8c (but outside of the square
framework). The dihedral angles between Ir4 plane and
pyrazine are 49.448 (48.828) and those between the Ir4 plane
and the phenyl rings of diisocyanides are 83.558 (83.588) and
patterns of macrocycles 8c and 8d in the solid state showed
that the cationic squares are stacked along the c axis, resulting
À
in long channel-like cavities. The Rh X bond lengths and
X-Rh-X' angles around the Rh atom for 8c and 8d are not
different from each other.
Crystal structure of 11bc: A perspective drawing of 11bc with
the atomic numbering scheme is given in Figure 4, and
selected bond lengths and angles are listed in Table 4. An
À
À
75.758 (75.958) The Ir1 Ir1* and Ir2 Ir2* diagonal lengths in
the rectangular structure are approximately 13.5 ä, similar to
those found for 8c.
Dimensions of cavity: The dimensions of the rectangular
cavity of complexes obtained here are summarized in Fig-
ure 5. On the basis of X-ray analyses, the complex 12bb
3.28 Å
11.6 Å
Cl
Ir
CN-R-NC
Ir
Rh
Rh
3.68 Å
N
N
Cl
7.00 Å
7.02Å for pyrazine
11.5Å for dipyridyl
7.92 Å
12.0Å
13.6 Å
Ir
CN-R-NC
Ir
Rh
Rh
Figure 5. The dimensions of cavity for tetranuclear complexes 8c, 8d, and
11bc.
surrounded by four diisocyanide ligand edges is estimated to
be a square structure with the dimensions of 11.7 Â 11.7 ä.
Complexes 11bd and 12bd, which both contain two di-
isocyanide and two 4,4-dipyridyl edges, are also calculated to
be a rectangular structure with the dimensions of 11.7 Â
11.5 ä.
In conclusion, the chemistry described above indicates the
stepwise formation and structures of the tetranuclear com-
plexes of iridium(iii) and rhodium(iii) that bear pentamethyl-
cyclopentadienyl groups and two different ligands. These new
types of tetranuclear complex are expected to play a role as
Figure 4. Complex cation of [{IrCl(Cp*)}4(m-1,4-(NC)2-2,3,5,6-Me4C6)2-
(m-pyrazine)2](CF3SO3)4 (11bc).
376
¹ WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002
0947-6539/02/0802-0376 $ 17.50+.50/0
Chem. Eur. J. 2002, 8, No. 2

Rh and Ir Macrocyclic Complexes
372 379
Me
Me
Me
Me
K[Ag(CN)2]
Ir
CN
NC
Ir
Ir
CN
NC
Ir
Cl
Cl
Me
Cl
Me
Cl
CN
Cl
Me
Me
Cl
CN
Scheme 3.
[{IrCl2(Cp*)}2(m-pyrazine)] (5c): Pyrazine c (8.8 mg, 0.11 mmol) was added
to solution of (80 mg, 0.10 mmol) in CH2Cl2 (10 mL) at room
the molecular architecture of supramolecules with ladder or
cubic frameworks.
a
1
temperature and stirred for 3 h. The resulting yellow precipitate
(73.4 mg, 83%) was separated and washed with diethyl ether. 1H NMR
(250 MHz, [D6]DMSO): d ˆ 1.62 (s, 30H; Cp*), 8.65 (s, 4H; pyradine);
elemental analysis calcd (%) for C24H34N2Cl4Ir2: C 32.88, H 3.91, N 3.20;
found: C 32.51, H 3.81, N, 3.27.
Experimental Section
[{RhCl2(Cp*)}2(m-pyrazine)] ¥ H2O (6c): This complex (orange, 281.0 mg,
82%) was obtained from 2 (302.6 mg, 0.49 mmol) and pyrazine c (43.1 mg,
0.54 mmol) by a procedure similar to that described for 5c. 1H NMR
(250 MHz, [D6]DMSO): d ˆ 1.61 (s, 30H, Cp*), 8.66 (s, 4H; pyradine);
elemental analysis calcd (%) for C24H34N2Cl4Rh2 ¥ H2O: C 40.25, H 5.07, N
3.91; found: C 40.29, H 4.84, N 4.04.
All reactions were carried out under a nitrogen atmosphere. Isocyanides
were prepared by modifing the literature method.[13] [{RhCl2(Cp*)}2] (1)
was prepared according to the literature method.[14] [{IrCl2(Cp*)}2] was
prepared by refluxing pentamethylcyclopentadiene and H2IrCl6 ¥ nH2O in
MeOH. Dichloromethane was distilled over CaH2 and diethyl ether was
distilled over LiAlH4. The IR spectra were measured on an FT/IR-5300
spectrometer. The 1H NMR spectra were measured at 250 MHz and
31P{1H} NMR spectra were measured at 101 MHz with 85% H3PO4 as an
external reference. Electrospray ionization (ESI) masss spectroscopy was
performed on a Parkin Elmer Sciex Instruments equipped by LC2Tune
1.2 software.
[{IrCl2(Cp*)}2(m-dipyridyl)] (5d): This complex (yellow, 139.3 mg, 82%)
was obtained from 1 (142.1 mg, 0.18 mmol) and dipyridyl d (30.6 mg,
0.20 mmol) by a procedure similar to that described for 5c. 1H NMR
(250 MHz,[D6]DMSO) d ˆ 1.62 (s, 30H, Cp*), 5.73 (s, CH2Cl2), 7.83 (d,
3J(H,H) ˆ 6 Hz, 4H; dipyridyl), 8.72 (d, 3J(H,H) ˆ 6 Hz, 4H; dipyridyl);
elemental analysis calcd (%) for C30H38N2Cl4Ir2 ¥ CH2Cl2: C 35.88, H 3.88, N
2.70; found: C 35.93, H 3.91, N 2.70.
Preparation of 1,4-diisocyano-2,5-dimethylbenzene (a): Diisopropylamine
(15 mL, 0.106 mol) was added to a solution of 2,5-dimethyl-1,4-phenyl-
enediformamide (2.9 g, 0.015 mol) in CH2Cl2 (100 mL). The mixture was
stirred for 20 min and POCl3 (5.0 mL, 0.054 mol) was added dropwise at
room temperature. The mixture was heated at 358C for 4 h. Aqueous
Na2CO3 (10%; 50 mL) was added at ice-cooling temperature and stirred
for 1 h. The organic layer was separated, and the aqueous layer was
extracted with CH2Cl2 (15 mL) three times. The CH2Cl2 solution was dried
over Na2SO4. The solvent was removed, and the residue was purified by
chromatography on alumina (containing 10% H2O), with benzene as an
eluant. The work-up of the eluate gave the title compound (1.58 g 68.7%).
Analogously, 1,4-diisocyano-2,3,5,6-tetramethylbenzene (70%) was pre-
pared from 2,3,5,6-tetramethyl-1,4-phenylenediformamide (6.6 g).
[{RhCl2(Cp*)}2(m-dipyridyl)] (6d): This complex (orange, 83.8 mg, 84%)
was obtained from 2 (80.0 mg, 0.13 mmol) and dipyridyl d (22.2 mg,
0.14 mmol) by a procedure similar to that described for 5c. 1H NMR
(250 MHz, [D6]DMSO): d ˆ 1.61 (s, 30H; Cp*), 5.73 (s, CH2Cl2), 7.83 (br,
4H; dipyridyl), 8.72 (br, 4H; dipyridyl); elemental analysis calcd (%) for
C30H38N2Cl4Rh2 ¥ 0.6CH2Cl2: C 44.54, H 4.79, N 3.39; found: C 44.42, H
5.21, N 3.36.
Preparation of tetranuclear complexes
[{Ir(m-Cl)(Cp*)}4(m-pyrazine)2](CF3SO3)4 (7c): Ag(CF3SO3) (31.1 mg,
0.12 mmol) in acetonitrile (10 mL) was added to
a solution of 5c
(50.9 mg, 0.06 mmol) in CH2Cl2 (10 mL) at room temperature and stirred
for 15 h. The solvent was removed, and the residue was extracted with
CH2Cl2, followed by filtration through a glass filter (G5) to remove
undissolved compounds. The filtrate was concentrated, and diethyl ether
was added, giving yellow crystals of 7c (43.8 mg, 64%). 1H NMR
(250 MHz, [D6]DMSO): d ˆ 1.58 (s, 30H; Cp*), 1.74 (s, 30H, Cp*), 2.05
(s, 12H; pyrazine), 8.84 (s, 4H; pyradine), 8.97 (s, 4H, pyrazine); elemental
analysis calcd (%) for C60H80N8Cl4F12O12S4Ir4: C 30.43, H 3.23, N 4.73;
found: C 30.24, H 3.48, N 4.59.
Preparation of dinuclear complexes
[{IrCl2(Cp*)}2{m-1,4-(NC)2-2,5-Me2C6H2}] (3a): Ligand
a
(49.5 mg,
0.32 mmol) was added to a solution of 1 (225.0 mg, 0.28 mmol) in CH2Cl2
(15 mL) at room temperature. After stirring for 3 h, the solvent was
concentrated and diethyl ether was added, giving yellow crystals of 3a
(198.4 mg, 75%). IR(nujol): nÄ ˆ 2137 cmÀ1
;
1H NMR (250 MHz, CDCl3):
d ˆ 1.86 (s, 30H; Cp*), 2.42 (s, 6H; Me), 7.29 (s, 2H; Ph); elemental analysis
calcd (%) for C30H38N2Cl4Ir2: C 37.81, H 4.02, N 2.94; found: C 37.26, H
4.04, N 2.97.
[{Rh(m-Cl)(Cp*)}4(m-pyrazine)2](CF3SO3)4 (8c): This complex (reddish
orange, 67%) was obtained from 6c (36.0 mg, 0.05 mmol) and Ag(CF3SO3)
(29.1 mg, 0.11 mmol) by a procedure similar to that described for 7c. FAB
[{IrCl2(Cp*)}2{m-1,4-(NC)2-2,3,5,6-Me4C6}] (3b): This complex (orange,
86%) was obtained from 1 (707 mg, 0.89 mmol) and ligand b (212.4 mg,
1.15 mmol) by a procedure similar to that described for 3a. FAB MS:
‡
MS m/z (%): 1254 (4) [M‡1] ; 1H NMR (250 MHz, [D6]DMSO): d ˆ 1.61
‡
(s, 60H; Cp*), 8.65 (s, 8H; pyrazine); elemental analysis calcd (%) for
C52H68N4Cl4F12O12S4Rh2: C 33.75, H 3.70, N 3.03; found: C 33.55, H 3.67, N
3.19.
m/z(%): 981 (5) [M‡1] ; IR(nujol): nÄ ˆ 2150 cmÀ1
;
1H NMR (250 MHz,
CDCl3): d ˆ 1.86 (s, 30H; Cp*), 2.39 (s, 12H; Me); elemental analysis calcd
(%) for C32H42N2Cl4Ir2: C 39.18, H 4.32, N 2.86; found: C 38.67, H 4.26, N
2.95.
[{Ir(m-Cl)(Cp*)}4(m-4,4'-dipyridyl)2](CF3SO3)4 (7d): This complex (yellow,
70.3 mg, 96%) was obtained from 5d (56.1 mg, 0.06 mmol) and Ag(CF3-
SO3) (33.3 mg, 0.13 mmol) by a similar procedure to that described for 7c.
1H NMR (250 MHz, [D6]DMSO): d ˆ 1.60 (s, 60H; Cp*), 8.25 8.96 (m,
16H; dipyridyl); elemental analysis calcd (%) for C64H76N4Cl4F12O12S4Ir2:
C 32.57, H 3.25, N 2.34; found: C 33.01, H 3.43, N 2.56.
[{RhCl2(Cp*)}2{m-1,4-(NC)2-2,3,5,6-Me4C6}] (4b): Diisocyanide b (59.7 mg,
0.32 mmol) was added to a solution of 2 (154.1 mg, 0.25 mmol) in CH2Cl2
(15 mL) at room temperature and stirred for 3 h. The solvent was
concentrated to about 3 mLand diethyl ether was added, giving 4b as
‡
anorange solid (146.5 mg, 73%). FAB MS: m/z (%): 802 (5) [M] .
IR(nujol): nÄ ˆ 2176 cmÀ1
;
1H NMR (250 MHz, CDCl3): d ˆ 1.83 (s, 30H;
[{Rh(m-Cl)(Cp*)}4(m-4,4'-dipyridyl)2](CF3SO3)4 (8d): This complex (red-
dish orange, 34.7 mg, 73%) was obtained from 6d (56.1 mg, 0.06 mmol)
and Ag(CF3SO3) (33.3 mg, 0.13 mmol) by a procedure similar to that
described for 7c. 1H NMR (250 MHz, [D6]DMSO): d ˆ 1.59, 1.61 (s, 60H;
Cp*), 7.91 8.89 (m, 16H; 4,4'-dipyridyl); elemental analysis calcd (%) for
C64H76N4Cl4F12O12S4Rh2: C 38.38, H 3.82, N 2.80; found: C 37.85, H 3.83, N
2.82.
Cp*), 2.40 (s, 12H; Me); elemental analysis calcd (%) for C32H42N2Cl4Rh2:
C 47.90, H 5.28, N 3.49; found: C 48.26, H 5.46, N 4.24.
[{RhCl2(Cp*)}2{m-1,4-(NC)-2,5-Me2C6H2}] (4a): This complex (orange,
73%) was obtained from 2 (142 mg, 0.23 mmol) and a (36.0 mg, 0.23 mmol)
by a procedure similar to that described for 4b. IR(nujol): nÄ ˆ 2160 cmÀ1
;
1H NMR (250 Hz, CDCl3): d ˆ 1.83 (s, 30H; Cp*), 2.44 (s, 6H; Me), 7.35 (s,
2H, Ar); elemental analysis calcd (%) for C30H38N2Cl4Rh2: C 46.54, H 4.95,
N 3.62; found: C 46.63, H 5.17, N 4.10.
[{Ir(m-Cl)(Cp*)}4{m-1,4-(NC)2-2,3,5,6-Me2C6}2](CF3SO3)4 (9b): This com-
plex (yellow crystals, 64.5 mg, 75%) was obtained from 3b (70.0 mg,
Chem. Eur. J. 2002, 8, No. 2
¹ WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002
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377

Y. Yamamotoa et al.
FULL PAPER
0.07 mmol) and Ag(CF3SO3) (40.4 mg, 0.16 mmol) by a similar procedure
[{IrCl(Cp*)}4{m-1,4-(NC)2-2,3,5,6-Me4C6}2(m-4,4'-dipyridyl)2](CF3SO3)4
(11bd): This complex (yellow, 38.7 mg, 70%) was obtained from 3b
(40.0 mg, 0.041 mmol), Ag(CF3SO3) (23.1 mg, 0.082 mmol), and bipyridyl
to that described for 7c. IR(nujol): nÄ ˆ 2186 cmÀ1 (N C); 1H NMR
ꢀ
(250 MHz, [D6]DMSO): d ˆ 1.94 (s, 60H; Cp*), 2.42 (s, 24H; Me);
elemental analysis calcd (%) for C68H84N4Cl4F12O12S4Ir2 ¥ 4MeCN:
C
(7.0 mg, 0.045 mmol) by a procedure similar to that described for 11bc.
1
IR(nujol): nÄ ˆ 2168 cmÀ1 (N C); H NMR (250 MHz,[D6]DMSO): d ˆ 1.77,
ꢀ
35.37, H 3.75, N 4.34; found: C 35.16, H 3.76, N 4.27.
1.80 (s, 60H; Cp*), 2.21 (s, 12H; Me), 2.31 (s, 12H; Me), 5.73 (s, CH2Cl2),
8.65 (s, 16H; dip); elemental analysis calcd (%) for C88H100N8Cl4F12O12-
S4Ir4 ¥ 3CH2Cl2: C 36.63, H 3.58, N 3.76; found: C 36.48, H 3.78, N 4.19.
[{Rh(m-Cl)(Cp*)}4{m-1,4-(NC)2-2,3,5,6-Me4C6}2](CF3SO3)4 (10b): This
complex (orange, 26.5 mg, 75%) was obtained from 4b (31.0 mg,
0.04 mmol) and Ag(CF3SO3) (20.8 mg, 0.08 mmol) by a similar procedure
to that described for 7c. IR(nujol): nÄ ˆ 2182 cmÀ1 (N C); 1H NMR
[{RhCl(Cp*)}4{m-1,4-(NC)2-2,3,5,6-Me4C6}2(m-4,4'-dipyridyl)2](CF3SO3)4
(12bd): This complex (orange, 22.3 mg, 33%) was obtained from 4b
(45.0 mg, 0.056 mmol), Ag(CF3SO3) (31.7 mg, 0.123 mmol), and 4,4'-
dipyridyl (9.6 mg, 0.062 mmol) by a procedure similar to that described
ꢀ
(250 MHz, [D6]DMSO): d ˆ 1.85 (s, 60H; Cp*), 2.37 (s, 24H; Me).
[{IrCl(Cp*)}4{m-1,4-(NC)2-2,3,5,6-Me4C6}2(m-pyrazine)2](CF3SO3)4 (11bc):
Ag(CF3SO3) (40.3 mg, 0.16 mmol) in acetonitrile (12 mL) was added to a
solution of 3b (70 mg, 0.07 mmol) in CH2Cl2 (10 mL) at room temperature
and stirred for 15 h. A solution of pyrazine (6.3 mg, 0.08 mmol) in CH2Cl2
was added to the mixture and stirred for 15 h. The solvent was removed and
the residue was extracted with CH2Cl2, followed by filtration through a
glass filter (G5) to remove insoluble compounds. The filtrate was
for 11bc. IR(nujol): nÄ ˆ 2182 cmÀ1 (N C); 1H NMR (250 MHz,
ꢀ
[D6]DMSO): d ˆ 1.85, 1.89 (s, 60H, Cp*), 2.40 (br, 12H; Me), 7.84 8.80
(m, 16H; dipy).
[{RhCl(Cp*)}4{m-1,4-(NC)2-2,3,5,6-Me4C6}4](CF3SO3)4 (12bb): This com-
plex (orange, 35.2 mg, 58%) was obtained from 4b (40.3 mg, 0.050 mmol),
Ag(CF3SO3) (28.4 mg, 0.10 mmol), and b (13.9 mg, 0.075 mmol) by a
procedure similar to that described for 11bc. IR(nujol): nÄ ˆ 2186 cmÀ1
concentrared to about 3 mLand diethyl ether was added, to give 11bc as
1
a yellow solid (39.1 mg, 59%). IR(nujol): nÄ ˆ 2176 cmÀ1 (N C); H NMR
ꢀ
(N C); 1H NMR (250 Mhz, [D6]DMSO): d 1.85, 1.87 (s, 60H, Cp*), 2.39
ꢀ
(250 MHz,[D6]DMSO): d ˆ 1.94 (s, 60H; Cp*), 2.42 (s, 2H; Me), 8.66 (s,
8H; pyrazine); elemental analysis calcd (%) for C76H92N8F12O12S4Cl4Ir4: C
34.78, H 3.53, N 4.27; found: C 34.87, H 3.71, N 4.61; ESI MS: m/z (%): 495
(br, 48H; Me); elemental analysis calcd (%) for C92H108N8Cl4F12O12S4Rh4 ¥
2CH2Cl2: C 43.47, H 4.35, N 4.31; found: C 43.74, H 4.58, N 4.71.
(5) [M]4‡, 475 (6) [M À pyrazine]4‡, 455 (94) [M À 2pyrazine]4‡
.
Reaction of 8c with 1,2-bis(diphenylphosphino)ethane (dppe): Dppe
(23.1 mg, 0.06 mmol) was added to a solution of 8c (50 mg, 0.03 mmol) in
MeOH (5 mL) and CH2Cl2 (5 mL) at room temperature and stirred for
15 h. The solution was concentrated to about 3 mLand diethyl ether was
added to give orange crystals of [RhCl(Cp*)(dppe)](OTf) (29.7 mg, 42%).
Concentration of the mother liquor and addition of diethyl ether gave
[{IrCl(Cp*)}4{m-1,4-(NC)2-2,5-Me2C6H2}2(m-pyrazine)2](CF3SO3)4 (11ac):
This complex (yellow, 39.1 mg, 59%) was obtained from 3a (50.0 mg,
0.05 mmol) and Ag(CF3SO3) (29.7 mg, 0.12 mmol) by a procedure similar
to that described for 11bc. IR(nujol): nÄ ˆ 2170 cmÀ1 (N C); 1H NMR
ꢀ
(250 MHz,[D6]DMSO): d ˆ 1.94 (s, 60H, Cp*), 2.42 (s, 24H; Me), 5.73 (s,
CH2Cl2), 7.96 (s, 4H; Ar), 8.65 (s, 8H; pyrazine); elemental analysis calcd
(%) for C74H88N8F12O12S4Cl4Ir4.CH2Cl2: C 33.65, H 3.33, N 4.30; found: C
33.39, H 3.63, N, 4.62.
‡
orange solid of 8c. FAB MS: m/z: 672 [M] . These complexes were
identified by comparison with spectroscopic data of the authentic
complexes.
[{RhCl(Cp*)}4{m-1,4-(NC)2-2,3,5,6-Me4C6}2(m-pyrazine)2](CF3SO3)4
(12bc): This complex (orange, 41.1 mg, 49%) was obtained from 4b
(60.0 mg, 0.07 mmol), Ag(CF3SO3) (42.3 mg, 0.15 mmol), and pyrazine
Reaction of 8c with mesityl isocyanide (MesNC): A mixture of 8c (53.9 mg,
0.03 mmol) and mesityl isocyanide (19.8 mg, 0.14 mmol) in acetonitrile
(10 mL) was stirred for 15 h at room temperature. The solution was
concentrated to about 3 mLand diethyl ether was added to give yellow
crystals of [RhCl(Cp*)(MesNC)2](OTf) (28.5 mg, 47%), identified by the
authentic complex obtained from the reaction of 2 with MesNC in the
presence of Ag(OTf). The presence of the starting material after workup of
the mother liquor was proven spectroscopically.
(6.7 mg, 0.08 mmol) by a similar procedure to that described for 11bc.
1
IR(nujol): nÄ ˆ 2186 cmÀ1 (N C); H NMR (250 MHz,[D6]DMSO): d ˆ 1.88
ꢀ
(s, 60H; Cp*), 2.43 (s, 24H; Me), 5.73 (s, CH2Cl2), 8.65 (s, 8H; pyrazine);
elemental analysis calcd (%) for C76H92N8Cl10F12O12S4Rh4 ¥ 3CH2Cl2: C
38.35, H 3.99, N 4.53; found: C 38.35, H 4.39, N, 4.20.
Table 5. Crystal data for 3a, 8c ¥ 2MeOH, 8d, and 11bc.
3a
8c ¥ 2MeOH
8d
11bc ¥ 4MeOH
formula
Mr
crystal system
space group
a [ä]
b [ä]
c [ä]
a [8]
b [8]
C30H38N2Cl4Ir
952.90
C54H76N4O14S4F12Cl4Rh4
1914.87
monoclinic
P21/n (No.14)
13.245(7)
20.417(6)
14.419(4)
90.0
108.31(2)
90.0
3701(1)
2
C68H88N4O16F12Cl4S4Rh4
2127.12
C78H98N8O14F12Cl4S4Ir4
2638.6
monoclinic
P21/n (No.14)
7.54(1)
16.571(7)
12.800(7)
90.0
95.69(7)
90.0
1590(2)
2
triclinic
triclinic
≈
≈
P1 (No.2)
P1 (No.2)
12.2258(9)
12.5307(9)
15.076(1)
114.3439(5)
91.9892(7)
95.143(1)
2089.2(2)
1
1.691
10.92
1072
0
13.1339(9)
16.203(1)
26.309(2)
73.953(2)
87.9327(7)
81.7369(6)
5324.7(6)
2
1.646
52.51
2564
0
g [8]
V [ä]
Z
1calcd [gcmÀ3
]
1.989
87.38
908
4
1.718
12.20
1920
4
m [cmÀ1
F(000)
]
scan rate [8minÀ1
]
reflections (<2q [8])
reflections observed [I > 2s(I)]
2915 (<50)
2798
6705 (<50)
6485[a]
9479 (<55)
8293
24272 (<55)
14760
parameters
R/Rw
R1
GOF[h]
172
433
513
1072
0.111/0.116[b]
0.041[d,e]
1.28
0.100/0.170[b]
0.050[d,f]
1.62
0.045/0.061[c]
0.045[c,g]
3.87
0.086/0.089[c]
0.086[c]
2.20
[a] [I > 10s(I)] [b] RˆS(Fo2 ÀFc2†/SFo2 ; Rw ˆ[Sw(Fo2 ÀFc2†2/SwF2o]1/2 (wˆ1/s2(Fo). [c] RˆR1ˆS(jjFo jÀjFc jj/SjFo j ; Rw ˆ[Sw(jFo jÀjFc j)2/SwF2o]1/2
(wˆ1/s2(Fo). [d] R1ˆS(jjFo jÀjFc jj/SjFo j. [e] For 2790 relections. [f] For [I > 2s(I)]. [g] For 8293 reflections. [h] GOFˆ[Sw(jFo jÀjFc j)2/S(nÀp)]1/2
where nˆnumber of data, pˆnumber of parameters.
,
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378

Rh and Ir Macrocyclic Complexes
372 379
X-ray crystallography–data collection: Complexes, 3a, 8c ¥ 2MeOH, 8d,
and 11bc ¥ 4MeOH were recrystallized from CH2Cl2/diethyl ether/MeOH
or CH2Cl2/diethyl ether/MeCN. Cell constants of 3a and 8c ¥ 2MeOH were
determined from 20 reflections on Rigaku four-circle automated diffrac-
tometer AFC5S. Data collection was carried out on a Rigaku AFC5S
refractometer at room temperature by using the 2q-w scan method.
Throughout the data collection the intensities of the three standard
reflections were measured every 200 reflections as a check of the stability
of the crystals and no decay was observed. An absorption correction was
applied with y scan methods. Crystals of 8d and 11bc were mounted at the
top of quartz fibers using perfluoro(polyoxypropylene ethylether), which
were set on a MSC/ADSC Quantum CCD/Rigaku AFC7 diffractometer
(8d) and on a MSC/ADSC Quantum CCD/Rigaku AFC8(ultraX 18)
diffractometer (11c). The measurements were made by using MoKa
radiation at À 908C to À 808C under a cold nitrogen stream. Four
preliminary data frames were measured at 0.58 increments of w, in order to
assess the crystal quality and preliminary unit cell parameters were
calculated. The cell parameters were refined using the all reflections
measured in the range 2.88 < 2q < 55.08. The intensity images were
measured at 0.58 intervals of w for a duration of 20 s for 8d and 108 s for
11bc. The frame data were integrated using a d*TREK program package,
and the data sets were corrected for absorption using a REQAB program.
The crystal parameters along with data collections are summarized in
Table 5. The data were corrected for Lorentz and polarization effects.
Atomic scattering factors were taken from Cromer and Waber with the
usual tabulation.[15] Anomalous dispersion effects were included in Fc;[16]
the values of Df' and Df'' were those of Creagh and McAuley.[17] All
calculations were performed using the teXsan crytallographic software
package.[18]
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[4] N. G. Naumov, A. V. Virovets, M. N. Sokolov, S. B. Artemkina, V. E.
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[5] T. Niu, X. Wang, A. Jacobson, Angew. Chem. 1999, 111, 2059 2062;
Angew Chem. Int. Ed. 1999, 38, 1934 1937.
[6] J. A. Lu, W. T. A. Harrison, A. J. Jacobson, Chem. Commun. 1996,
399 402.
[7] J. Cernak, J. Chomic, O. Ori, G. D. Andreeti, Acta Crystallogr. Sect. C
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[8] K. K. Klausmeyer, T. B. Rauchfuss, S. R. Wilson, Angew. Chem. 1998,
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2000, 1801 1802.
[12] T. Rajendran, B. Manimaran, G.-H. Lee, S.-M. Peng, C. M. Wang, K.-
L. Lu, Inorg. Chem. 2000, 39, 2016 2017.
[13] R. Obrecht, R. Herrmann, I. Ugi, I. Synthesis 1985, 400 402.
[14] J. W. Kang, K. Moseley, M. Maitlis, J. Am. Chem. Soc. 1969, 91, 5971
5977.
Determination of the structures: All structures were solved by Patterson
methods. The positions of all non-hydrogen atoms except the solvent
molecules were refined with anisotropic thermal parameters by using full-
matrix least-squares methods. All hydrogen atoms were calculated at the
À
ideal positions with the C H distance of 0.95 ä.
Crystallographic data (excluding structure factors) for the structures
reported in this paper have been deposited with the Cambridge Crystallo-
graphic Data Centre as supplementary publication no. CCDC-151901 (3a),
CCDC-151902 (8c), CCDC-151903 (11bc), and CCDC-171089 (8d).
Copies of the data can be obtained free of charge on application to CCDC,
12 Union Road, Cambridge CB21EZ, UK (fax: (‡44)1223-336-033;
e-mail: deposit@ccdc.cam.ac.uk).
Acknowledgement
[15] D. T. Cromer, J. T. Waber, International Tables for X-ray Crystallog-
raphy, Kynoch, Birmingham (England), 1974, Table 2.2A.
[16] J. A. Ibers, W. C. Hamilton, Acta Crystallogr. 1964, 17, 781 785.
[17] D. C. Creagh, W. J. McAuley, International Tables for Crystallography,
Vol. C, Kluwer, Boston, 1992 Table 4.2.6.8, pp. 219 222.
[18] TEXSANX: Crystal Structure Analysis Package, Molecular Structure
Corporation Houston, TX, 1985 and 1992.
This work was partially supported by the Grant-in-Aid for Scientific
Research from the Ministry of Education, Science, Culture, and Sports,
Japan (12640545).
[1] a) ™Supramolecular Architecture∫: R. Robson, B. F. Abrahams, S. R.
Batten, R. W. Gable, B. F. Hoskins, J. Liu, ACS Symp. Ser. 1992, 499,
Received: July 4, 2001 [F3395]
Chem. Eur. J. 2002, 8, No. 2
¹ WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002
0947-6539/02/0802-0379 $ 17.50+.50/0
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