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Graphical Abstract Angew. Chem. Int. Ed. 192003

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Contents
Web Sites
http://www2.chemie.uni-erlangen.de/
services
2110
Quantum Chemistry: A Playground with
Hidden Treasures
C. van Wllen
Books
Ionic Liquids in Synthesis
2111
Peter Wasserscheid, Tom Welton
reviewed by M. Maase
Encyclopedia of Catalysis
2112
Istvan T. Horvath
reviewed by C. D. Frohning
Highlights
Mechanisms of Acid Dissociation
A. F. Voegele, K. R. Liedl*
2114 – 2116
Exploring HBr Ionization at the Molecular
Level
Cluster techniques and femtosecond
spectroscopy has been used in a recent
study to elucidate the mechanism of HBr
dissolution and ionization. Complete dissolution is achieved by a cluster of five
water molecules, while photoinduced
electric excitation is necessary in clusters
of four water molecules. The findings are
in good agreement with ab initio results
which propose that total dissolution can
be achieved in clusters of four water
molecules (see structure).
Stabilizing Carbenes
W. Kirmse*
Br
Ph
2117 – 2119
.
.
F3C
.
.
Ph
Br F3C
Persistent Triplet Carbenes
1
t1/2 = 19 min at 20°C
Unpairing carbenes with unpaired electrons: Triplet carbenes are prone to
dimerization but can be stabilized kinetically. By means of steric shielding and
electron delocalization, Tomioka and co-
2
t1/2 = 9 min at 20°C
workers succeeded in preparing exceptionally long-lived triplet diarylcarbenes,
such as 1 and the bromine- and trifluoromethyl 2.
Reviews
Cyclin-Dependent Kinases
A. Huwe, R. Mazitschek,
A. Giannis*
A basic approach to cancer therapy:
Cyclin-dependent kinases (CDKs) and
their activating subunits, the cyclins, are
the central pacemakers of the cell cycle.
Virtually all malignant diseases are ascribed to a defect of these key players or their
direct regulators. Therefore, great efforts
have been made to synthesize compounds which modulate the activity of
CDKs. This review provides an overview of
the progress in the development of lowmolecular-weight CDK inhibitors, such as
the natural product stauosporin (1).
2122 – 2138
Small Molecules as Inhibitors of CyclinDependent Kinases
2102
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2003, 42, 2102 – 2108
Angewandte
Chemie
Communications
Artificial Light-Harvesting Antenna
T. S. Balaban,* A. D. Bhise, M. Fischer,
M. Linke-Schaetzel, C. Roussel,
N. Vanthuyne
2140 – 2144
Controlling Chirality and Optical Properties of Artificial Antenna Systems with
Self-Assembling Porphyrins
In a biomimetic approach, the same
groups that are responsible for the selfassembly of bacteriochlorophylls in the
natural antenna systems of green photosynthetic bacteria, have been engineered
onto desired positions of fully synthetic
porphyrins. The architecture of the monomeric building block determines both the
chirality and the optical properties of the
supramolecular assembly, depicted right,
as a tetramer. Neither the self-assembly,
nor the chemisorption onto titania nanoparticles quenches the fluorescence of the
aggregates, thus they may be of use in
dye-photosensitized solar cells.
Multicomponent Asymmetric Catalysts
T. Arai, T. Sekiguti, K. Otsuki, S. Takizawa,
H. Sasai*
2144 – 2147
“Catalyst Analogue”: A Concept for Constructing Multicomponent Asymmetric
Catalysts (MAC) by Using a Polymer
Support
Big MAC news! A new concept for
constructing multicomponent asymmetric catalysts (MACs) is proposed by use of
a stable “catalyst analogue”. After
copolymerization of a catalyst analogue
having olefinic moieties with a monomer
(e.g., methyl methacrylate), the resulting
polymer is used to prepare an active
catalyst by exchanging the connecting
group with a catalytically active metal (see
scheme).
Li-Intercalated TiS2 Nanotubes
Filling the gaps: A low-temperature solution route was employed to successfully
prepare multiwalled TiS2 nanotubes with
open-ended tips (see HRTEM image). The
as-prepared nanotubes could be intercalated with lithium atoms by treating a
solution of the TiS2 nanotubes with
nBuLi. The resulting homogeneous intercalated phase of LiTiS2 exhibited a c-axis
expansion of approximately 10.5 % relative to the original TiS2 material.
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ANGEWANDTE CHEMIE International
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Angew. Chem. Int. Ed. 2003, 42, 2102 – 2108
J. Chen,* Z.-L. Tao, S.-L. Li
2147 – 2151
Lithium Intercalation in Open-Ended TiS2
Nanotubes
postage paid at Jamaica NY 11431. US POSTMASTER: send address changes to Angewandte
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are retired or self-employed consultants, print
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Europe E 248.00/Outside Europe US$ 348.00.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2103
Contents
Ruthenium Oxide Surface Chemistry
[110]
J. Wang, C. Y. Fan, Q. Sun, K. Reuter,
K. Jacobi,* M. Scheffler,
G. Ertl
2151 – 2154
[001]
[110]
Surface Coordination Chemistry:
Dihydrogen versus Hydride Complexes on
RuO2(110)
Both atomic and molecular hydrogen are
found to chemisorb together at the rutilestructure RuO2(110) single crystal surface
(depicted) at 85 K. The combination of
low-temperature ultrahigh vacuum vibra-
tional spectroscopy in conjunction with
DFT calculations provides detailed insight
into the coordination chemistry of a solid
oxide surface (O: green, Ru: violet).
Very different electronic properties are
found in the hexagonal and lamellar
nanocomposite films (see schematic
representations) prepared by dilution of a
pyrrole-containing surfactant with non-
polymerizable surfactants in a sol–gelbased template polymerization. The hexagonal composite film comprises a thin
polypyrrole nanocable covered with an
insulating silicate channel.
Reactions within crystals: Homochiral
oligo(phenylalanine)s (see MALDI-TOF
mass spectrum) were obtained from a
racemic monomer by utilizing a “zipperlike” mechanism in the solid state (see
packing diagram). By generating such
species within crystalline architectures,
the formation of oligopeptides of up to
17 units in length is plausible.
Nanocomposite Films
M. Ikegame, K. Tajima,
T. Aida*
2154 – 2157
Template Synthesis of Polypyrrole Nanofibers Insulated within One-Dimensional
Silicate Channels: Hexagonal versus
Lamellar for Recombination of Polarons
into Bipolarons
Oligopeptide Formation in Crystals
J. G. Nery, G. Bolbach, I. Weissbuch,*
M. Lahav*
2157 – 2161
Generation of Oligopeptides with Homochiral Sequences by Topochemical Reactions within Racemic Crystals of Phenylalanine-N-carboxyanhydride
Dynamic Trimetallic Clusters
W. Schuh, P. Braunstein,* M. BKnard,
M.-M. Rohmer, R. Welter
2161 – 2164
An Unusual Dynamic Fe-Hg-Pd Cluster
with a Palladium(0) Fragment Stabilized
by d10–d10 Heterometallic Bonding
2104
A heterometallic tetranuclear cluster
resulting from an unprecedented metal–
metal interaction is described in which a
14-electron PdL2 fragment is bonded to a
Fe-Hg-Fe chain through helically arranged
diphenylphosphanylmethane ligands (see
picture), along which it exhibits an oscillating motion. The cluster exhibits a close
contact between the Pd0 and HgII centers;
the first such d10–d10 interaction to have
been observed.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
(OMe)3
Si
O
C
Ph2P
(OC)2Fe
Ph2P
Hg
PPh2
Fe(CO)3
Pd
Si(OMe)3
PPh2
Angew. Chem. Int. Ed. 2003, 42, 2102 – 2108
Angewandte
Chemie
Dendrimers as guests: Dendrimers containing a single 4,4’-bipyridinium residue
covalently attached to the focal points of
carboxylate-terminated dendrons are
strongly complexed by cucurbit[7]uril in
aqueous solution (see schematic representation). The complexation has been
monitored and quantified by NMR spectroscopic, UV/Vis spectroscopic, and
mass spectometric techniques.
Host-Guest Binding Interactions
W. Ong, A. E. Kaifer*
2164 – 2167
Molecular Encapsulation by Cucurbit[7]uril of the Apical 4,4’-Bipyridinium
Residue in Newkome-Type Dendrimers
Cu-Catalyzed Couplings
X. Xie, P.-W. Phuan,
M. C. Kozlowski*
Unusually orderly! Alkynylnaphthols
undergo two kinds of couplings stepwise,
with high stereocontrol, and in one pot to
give chiral binaphthyl polymers like that
shown. Since the chemoselectivity of each
coupling is remarkably high, this
approach is useful for the organized
assembly of multifunctional substrates in
a single operation.
2168 – 2170
Novel Pathways for the Formation of
Chiral Binaphthyl Polymers: Oxidative
Asymmetric Phenolic Coupling Alone and
in Tandem with the Glaser–Hay Coupling
Synthetic Peptides
Y. Krishnan-Ghosh,
S. Balasubramanian*
2171 – 2173
Dynamic Covalent Chemistry on SelfTemplating Peptides: Formation of a
Disulfide-linked b-Hairpin Mimic
Driving peptides round the bend: Thiolcontaining linear peptides (ASH and BSH)
are dimerized (see scheme) using
dynamic covalent chemistry to preferentially form an energetically stabilized
disulfide by a self-templating mechanism.
NMR spectroscopy experiments on this
disulfide show that the stabilization is a
result of b-sheet formation with the
disulfide bond acting as a turn scaffold
yielding a peptide with a hairpin-type
conformation.
A Polyoxothiometalate Tetramer
Fours for thought: The title compound
was prepared by condensation of the
preformed unit {Mo2O2S2}2+ as a linker on
to the trivacant anion [a-P2W15O5]12. The
self-assembled structure exhibits a modular arrangement (see structure). 31P and
183
W NMR spectroscopy revealed that the
structure of the supramolecular tetra-unit
anion was maintained in solution.
Angew. Chem. Int. Ed. 2003, 42, 2102 – 2108
E. Cadot,* M.-A. Pilette, J. Marrot,
F. SKcheresse
2173 – 2176
A Supramolecular Tetra-Dawson Polyoxothiometalate: [(a-H2P2W15O56)4{Mo2O2S2(H2O)2}4{Mo4S4O4(OH)2(H2O)}2]28
www.angewandte.org
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2105
Contents
PR2
Zirconium Spirophosphanes
P
K. Owsianik, M. Zablocka,* B. Donnadieu,
J.-P. Majoral*
2176 – 2179
N
P
P
Ph
ZrCp2
Cl
N
The reaction of a trichloro iminophosphorane (Cl3P¼NtBu) and either a
zirconaindane phospholane or an azazirconaindane phosphane proceeds in an
unexpected fashion, with the trapping of a
transient chlorophosphaimine species
(ClP¼NtBu), and the formation of
unique metalla-azaspirophosphanes (see
picture).
N
ZrCp2
Cl
Metalla-Azaspirophosphanes: Synthesis,
Structure, and Reactivity
Photolysis of Tungsten Complexes
R. Krishnan, H. E. Gottlieb,
R. H. Schultz*
2179 – 2181
Furans Bound Face-On: Sequential Loss
of CO in the Formation of
[W(CO)4(h4-2,5-dimethylfuran)]
and activation parameters of its formation
from the unstable precursor [(CO)5W(h1Me2Fur)] (1) are measured by using timeresolved infrared absorption spectroscopy.
An unusual coordination mode is proposed for the furan ligand in the complex
[(CO)4W(h4-Me2Fur)] (2; Me2Fur = 2,5dimethylfuran), which is produced by
photolysis of a solution of [W(CO)6] in the
presence of excess Me2Fur. The kinetics
Metal-Free Electron Microscopy
No metal jacket required: The surface
structures of mesoporous materials were
accurately determined by using electronmicroscopy techniques—without the
need for metal plating. The effectiveness
of these techniques was demonstrated
with SBA-15 mesoporous silica (see
image) and its CMK-5 carbon replica, for
which high-resolution images of the surfaces were obtained.
S. Che, K. Lund, T. Tatsumi, S. Iijima,
S. H. Joo, R. Ryoo,
O. Terasaki*
2182 – 2185
Direct Observation of 3D Mesoporous
Structure by Scanning Electron Microscopy (SEM): SBA-15 Silica and CMK-5
Carbon
Ar
Pt Complexes of N-Confused Porphyrin
Ar
N
NH
Facile Formation of N-Confused Porphyrin
Dimers by Platinum(ii) Coordination to
the Outer-Nitrogen Atoms
N
Ar
Ar
NH
N
Cl
Ar
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
HN
NH
R
N
www.angewandte.org
Ar
Pt
Ar
R
Confusion but no doubt: Two types of PtII
dimer complexes of N-confused porphyrin
(depicted) were synthesized and the
structures were unequivocally elucidated
by X-ray crystal analyses. Both complexes
2106
N
Ar
Pt
Ar
HN
N
Ar
HN
Ar
H. Furuta,* K. Youfu, H. Maeda,
A. Osuka*
2186 – 2188
Ar
Cl
N
NH
HN
N
Ar
Ar
contain a metallocycle that binds to a Pt
center by an outer-nitrogen atom of the
confused porphyrin, and by an orthocarbon atom of a meso-aryl group.
Angew. Chem. Int. Ed. 2003, 42, 2102 – 2108
Angewandte
Chemie
The gradual transition from cylindrical
micelles to vesicles on increasing the
temperature is demonstrated in the cationic–anionic surfactant system of
sodium dodecylsulfate/dodecyltriethylammonium bromide. The transition has
been studied by dynamic light scattering
studies (see graph), a freeze-fracture
technique with observation by electron
microscopy, and rheology measurements.
Iodine(iii) crowned: Slow evaporation of
solvents afforded the 1:1 complex 1
between [HCCIPh]BF4 and
[18]crown-6 (18C6). Both the solid-state
and solution structures of 1 were determined. Reaction of 1 with methanol
proceeds in a Michael-type fashion. The
complexation with 18C6 increases the
stability of labile l3-iodanes, such as 1.
Amides of 2-iodoxybenzoic acid (IBX
amides, 1) are a new class of pentavalent
iodine compounds with a pseudo-benziodoxole structure. These 2-iodoxybenzamides are useful reagents for the oxidation of alcohols, with a reactivity pattern
similar to IBX (R = CH(CH3)CO2CH3 or
CH(CH2Ph)CO2CH3 (in crystal structure
shown)).
Micelle to Vesicle Transition
H. Yin, Z. Zhou, J. Huang,* R. Zheng,
Y. Zhang
2188 – 2191
Temperature-Induced Micelle to Vesicle
Transition in the Sodium Dodecylsulfate/
Dodecyltriethylammonium Bromide
System
Methanol Additions and Iodanes
M. Ochiai,* K. Miyamoto, T. Suefuji,
S. Sakamoto, K. Yamaguchi,
M. Shiro
2191 – 2194
Synthesis, Characterization, and Reaction
of Ethynyl(phenyl)-l3-Iodane Complex
with [18]Crown-6
Oxidation of Alcohols
V. V. Zhdankin,* A. Y. Koposov,
B. C. Netzel, N. V. Yashin, B. P. Rempel,
M. J. Ferguson,
R. R. Tykwinski*
2194 – 2196
IBX Amides: A New Family of Hypervalent
Iodine Reagents
Communications labeled with this symbol have been judged by two referees as being “very important papers”.
The publication of Communications labeled with this symbol has been accelerated because of their topical or highly competitive
nature.
Service
Angew. Chem. Int. Ed. 2003, 42, 2102 – 2108
www.angewandte.org
Keywords
2198
Authors
2199
Vacancies
2197
Preview
2201
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2107
Contents
Apology
*
In the Communication “Nanoporous
Lanthanide–Copper(ii) Coordination Polymers: Syntheses and Crystal Structures of
[{M2(Cu3(iminodiacetate)6)} · 8 H2O]n
(M = La, Nd, Eu)” by Y.-P. Ren, L.-S. Long,
et al. (Angew. Chem. 2003, 115, 550;
Angew. Chem. Int. Ed. 2003, 42, 532) the
authors missed important references:
“Synthesis, Crystal Structure and Magnetic Properties of a Series of Polymeric
Lanthanoid–Copper Complexes
[Ln2Cu3{O(CH2CO2)2}6] · n H2O (Ln = La,
2108
Nd, n = 9; Ln = Er, n = 6)” (J. G. Mao, J. S.
Huang, J. F. Ma, J. Z. Ni, Trans. Met.
Chem. 1997, 22, 277–280), “Synthesis and
Crystal Structure of a Novel Lanthanide–
Copper Mixed Metal Complex:
Gd2Cu3{O(CH2COO)2}6 · 9 H2O” (J. G.
Mao, L. Song, X. Y. Huang, J. S. Huang,
Polyhedron 1997, 16, 963–966), “Synthesis
and Structural Characterization of a Novel
Polymeric Gadolinium(iii)–Copper(ii)
Complex of Iminodiacetic Acid” (J. G.
Mao, L. Song, J. S. Huang, J. Chem.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Crystallogr. 1998, 28, 475–479), and “Synthesis and Crystal Structure of a New
Praseodymiun(iii)–Copper(ii) Polymeric
Complex: [Pr2(Cu3(L1)6)n]
(H2L1 = NH{CH2COOH}2)” (J. G. Mao, L
Song, J. S. Huang, Chinese J. Struct. Chem.
1999, 18, 4–8). The authors apologize for
this oversight and thank Qinde Liu of
Queen’s University, Canada, and Prof.
J. G. Mao, Fuzhou, China, for bringing it to
their attention.
Angew. Chem. Int. Ed. 2003, 42, 2102 – 2108
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