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Graphical Abstract Angew. Chem. Int. Ed. 392004

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Contents
The following Communications are available online (in Wiley InterScience). You can find them, as
well as forthcoming Reviews, Highlights, and Essays, at www.angewandte.org, under Early View.
E. Hevia, G. W. Honeyman, A. R. Kennedy, R. E. Mulvey,*
D. C. Sherrington:
Synergic Monodeprotonation of Bis(benzene)chromium by
Using Mixed Alkali Metal–Magnesium Amide Bases and Structural Characterization of the Heterotrimetallic Products
DOI: 10.1002/anie.200460637
Published online: September 7, 2004
J. M. Herrera, V. Marvaud,* M. Verdaguer, J. Marrot, M. Kalisz,
C. Mathoni're*:
Reversible Photoinduced Magnetic Properties in the Heptanuclear Complex [MoIV(CN)2(CN CuL)6]8+: A Photomagnetic HighSpin Molecule
DOI: 10.1002/anie.200460387
Published online: September 3, 2004
Articles judged by the referees or the editor as being either very important or very urgent are immediately edited, proof-read, and electronically
published once the manuscript has arrived in the editorial office in its final form. As long as there is no page number available these articles should
be cited in the following manner:
Author(s), Angew. Chem. Int. Ed., online publication date, DOI.
News
Organic Synthesis:
K. C. Nicolaou Receives
Arthur C. Cope Award
5116
Hydrocarbon Chemistry:
G. A. Olah Awarded
Priestley Medal
5116
Books
Handbook of Size Exclusion
Chromatography and Related Techniques
Chi-San Wu
reviewed by B. Trathnigg
5117
Basic Atomic and Molecular Spectroscopy
J. Michael Hollas
reviewed by D. Smith
5117
Highlights
Molecular Electronics
R. A. Wassel,
C. B. Gorman*
5120 – 5123
Establishing the Molecular Basis for
Molecular Electronics
5106
Molecular structure–property relationships for molecular electronics are beginning to emerge. Recent experiments lend
credibility to the single-molecule nature of
transport measurements and illustrate the
molecular features that give rise to various interesting conductance behaviors
(see picture).
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 5106 – 5115
Angewandte
Chemie
Porphyrinoid Complexes
Molecular mitosis: Figure-eight octaphyrins form binuclear metal complexes that
can split into two covalently spiro-linked
corrolates. In a unique case binuclear CuII
[36]octaphyrin divides thermally into two
CuII [18]porphyrins presumably with participation of a transient spirocyclobutane
species (see schematic representation).
L. Latos-Grażyński*
5124 – 5128
Bimetallic Figure-Eight Octaphyrins Split
into Four-Pyrrolic Macrocycles
Minireviews
Species of curiosity for a long time and
more recently ligands for metals, nucleophilic heterocyclic carbenes deserve
renewed attention as reagents and catalysts in organic synthesis. Their known
chemistry (see scheme) foretells an
impressive future.
Carbene Reagents
V. Nair,* S. Bindu,
V. Sreekumar
5130 – 5135
N-Heterocyclic Carbenes: Reagents, Not
Just Ligands!
Reviews
Asymmetric Catalysis
P. I. Dalko,* L. Moisan
5138 – 5175
In the Golden Age of Organocatalysis
Metal-free synthesis: An increasing
number of asymmetric organic reactions
can be catalyzed by a chiral organic
molecule. Although substrate dependency
remains an important issue in many
cases, a large number of organocatalytic
transformations are as efficient as current
standards in asymmetric synthesis
demand (see example).
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Angew. Chem. Int. Ed. 2004, 43, 5106 – 5115
www.angewandte.org
individuals who are personal members of a
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already subscribes, or who are retired or selfemployed consultants, print only: Europe
E 248.00/outside Europe US$ 378.00. Postage
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prices are exclusive VAT.
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5107
Angewandte
Chemie
Communications
Dendrimer Synthesis
Fruits of the laboratory: Dendrimers containing up to six different functional
groups can be prepared in multistep onepot reactions by using a selective manipulation and deprotection strategy (see
example). The authors call these multifunctional dendrimers molecular fruitsalad trees; they could function as useful
building blocks for drug-delivery systems
and novel materials.
M. B. Steffensen,
E. E. Simanek*
5178 – 5180
Synthesis and Manipulation of
Orthogonally Protected Dendrimers:
Building Blocks for Library Synthesis
Bioorganic Chemistry
A. Zumbuehl, D. Jeannerat, S. E. Martin,
M. Sohrmann, P. Stano, T. Vigassy,
D. D. Clark, S. L. Hussey, M. Peter,
B. R. Peterson, E. Pretsch, P. Walde,
E. M. Carreira*
5181 – 5185
Not only skin deep: A fluorescein–
amphotericin B conjugate with a new
piperazine linker (see structure) was prepared and used as a probe of the biomembrane and the mechanism of action
of amphotericin B both in vivo and in
liposomal experiments. The amphotericin B analogue localizes at the membrane
of yeast cells but is internalized by
mammalian cells.
Hair raising! Poly(methyl methacrylate)
chains grown on a dendronized polymer
(denpol) having repeat units with terminal
2-bromoisobutyramide groups produce a
hairy surface. When adsorbed on mica,
MoS2, and highly oriented pyrolytic
graphite, the hairy denpol molecules have
a quasi two dimensional backbone
conformation. The 50-nm-long hairs
bend back on the MoS2 (see image) and
graphite substrates.
An Amphotericin B–Fluorescein
Conjugate as a Powerful Probe for
Biochemical Studies of the Membrane
Radical Polymerization
A. Zhang, J. Barner, I. GMessl, J. P. Rabe,*
A. D. SchlNter*
5185 – 5188
A Covalent-chemistry Approach to Giant
Macromolecules and Their Wetting
Behavior on Solid Substrates
Enzyme Activity
H. D. Mootz, E. S. Blum,
T. W. Muir*
A protein rheostat: A strategy for controlling enzyme activity by cleavage of a lowaffinity “pseudosubstrate” inhibitor from
an autoregulated version of the enzyme
(see figure) is described. Peptide-bond
Angew. Chem. Int. Ed. 2004, 43, 5106 – 5115
cleavage was mediated by conditional
protein splicing. The small molecule
rapamycin was used to induce intein
trans-splicing of the catalytic subunit of
cAMP-dependent protein kinase A (PKA).
www.angewandte.org
5189 – 5192
Activation of an Autoregulated Protein
Kinase by Conditional Protein Splicing
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5109
Contents
Supercritical Fluids
A new, general and objective approach to
locating critical points of fluid mixtures is
described (see picture). It is new because
it exploits the fact that the liquid phase
forms preferentially on the surface of the
sensor. It is general because it can be used
with any type of surface-sensitive sensor,
and it is objective because it is based on
the numerical output of a sensor rather
than the visual image normally used for
phase equilibrium studies.
J. Ke,* R. M. Oag, P. J. King, M. W. George,
M. Poliakoff*
5192 – 5195
Sensing the Critical Point of HighPressure Mixtures
Understanding frustration: The control of
structure through the choice of the template has allowed the synthesis of nonanuclear metal wheels that contain {Cr8Ni}
or {Cr7(VO)2} cores. Magnetic studies
(see picture) of one of these wheels shows
that it behaves as a magnetic MMbius
strip. These are the first detailed magnetic
studies of an odd-numbered ring larger
than trinuclear and should help in the
understanding of spin-frustrated systems.
Magnetic Properties
O. Cador, D. Gatteschi, R. Sessoli,*
F. K. Larsen, J. Overgaard, A.-L. Barra,
S. J. Teat, G. A. Timco,*
R. E. P. Winpenny*
5196 – 5200
The Magnetic MMbius Strip: Synthesis,
Structure, and Magnetic Studies of
Odd-Numbered Antiferromagnetically
Coupled Wheels
Gas–Surface Interactions
Molecular gymnastics: Ethylene molecules (C atoms in green) rotating along
the principal axes impinge perpendicularly
on an Ag (001) metal surface precovered
with O2 (O atoms in red) and may stick in
some favorable cases. The sticking probability S depends on the approach of the
C=C bond to the surface: “helicopters”
(d) stick better than “cartwheels” (b and
c) or “cigars” (a).
L. Vattuone,* A. Gerbi, M. Rocca,
U. Valbusa, F. Pirani, F. Vecchiocattivi,
D. Cappelletti
5200 – 5203
Stereodynamic Effects in the Adsorption
of Ethylene onto a Metal Surface
Fluorinated Alkenes
G. K. S. Prakash,* J. Hu, Y. Wang,
G. A. Olah
5203 – 5206
Difluoromethyl Phenyl Sulfone, a Difluoromethylidene Equivalent: Use in the
Synthesis of 1,1-Difluoro-1-alkenes
5110
A nucleophilic substitution–elimination
reaction strategy in which difluoromethyl
phenyl sulfone is used as a selective
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
difluoromethylidene equivalent allows the
facile synthesis of 1,1-difluoro-1-alkenes
from primary alkyl halides (see scheme).
Angew. Chem. Int. Ed. 2004, 43, 5106 – 5115
Angewandte
Chemie
Materials Science
Gutsy chemistry: A solvothermal process
has been developed for the controlled
creation of interior space in TiO2 intestines (either hollow (see TEM image) or
partially filled) or spheres in the anatase
polymorph. A morphological transformation from intestine to sphere is observed
when the water content of the water/2propanol mixture is decreased.
H. G. Yang, H. C. Zeng*
5206 – 5209
Creation of Intestine-like Interior Space for
Metal-Oxide Nanostructures with a
Quasi-Reverse Emulsion
Superhydrophobic Films
K. Acatay, E. Simsek, C. Ow-Yang,
Y. Z. Menceloglu*
5210 – 5213
Dry films: An electrospinning process was
used to form films with high water contact
angles (166.78) and low sliding-angles
(4.38). The electrospun films exhibit
excellent superhydrophobic Cassie-regime
stability: The figure shows a nonwetting
water droplet, even after 400 Pa of uniaxial
loading.
Stable! The first stable salts containing a
simple, inorganic cation with an N Cl
bond are prepared (see picture). They are
[NH3Cl]+[BF4] , [NH3Cl]+[AsF6] , and
[NH3Cl]+[SbF6] and can be safely prepared from (Me3Si)2NCl in mixtures of HF
and the corresponding Lewis acids and
could be used as storable generators for
monochloramine gas.
The bigger the better: Increasing metal
size seems to be the determining factor in
the formation of an unprecedented series
of homoleptic linear pyrazolates of the
heavy alkaline-earth metals (Ca, Sr, Ba, see
picture, Ba = green, N = blue, C = black),
with the formation of trinuclear calcium,
tetranuclear strontium, and hexanuclear
barium derivatives. The linear oligomers
display a noteworthy array of metal–ligand
bonds.
Tunable, Superhydrophobically Stable
Polymeric Surfaces by Electrospinning
Inorganic Cations
S. Schneider,* R. Haiges, T. Schroer,
J. Boatz, K. O. Christe*
5213 – 5217
The [NH3Cl]+ Ion
Alkaline-Earth-Metal Complexes
J. Hitzbleck, G. B. Deacon,*
K. Ruhlandt-Senge*
5218 – 5220
Linear Finite “Mers”—Homoleptic
Polynuclear Heavy Alkaline Earth Metal
Pyrazolates
Carbohydrates
X. Huang,* L. Huang, H. Wang,
X.-S. Ye*
5221 – 5224
Iterative One-Pot Synthesis of
Oligosaccharides
Straight to the point! Preactivation of a
p-tolyl thioglycoside donor, followed by
sequential addition of p-tolyl thioglycosyl
acceptors in one reaction flask allowed
rapid syntheses of oligosaccharides
Angew. Chem. Int. Ed. 2004, 43, 5106 – 5115
independent of anomeric reactivities of
donors and acceptors (see scheme). This
strategy greatly streamlines the assembly
of oligosaccharides.
www.angewandte.org
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5111
Contents
Titanium Complexes
P. J. Alonso, L. R. Falvello, J. ForniVs,
M. A. GarcWa-Monforte,
B. MenjXn*
5225 – 5228
A Five-Coordinate Homoleptic
Organotitanium(iii) Compound
Reversed Berry pseudorotation (see
picture) results in a severely distorted
trigonal-bipyramidal geometry with C2v
symmetry in the paramagnetic (d1) anion
[Ti(C6F5)5]2 , which was obtained by the
low-temperature reaction of TiCl4·x Et2O
and LiC6F5 and is the first homoleptic
organometallic compound containing a
[TiR5]2 unit.
Asymmetric Catalysis
K. P. Bryliakov,* E. P. Talsi
Catalytic converter: A (salen)iron(iii)
complex (salen* = asymmetric bis(salicylidene)ethylenediamine ligand) can be
used as a catalyst system for the asymmetric oxidation of aryl sulfides by iodosylbenzene (see scheme). An iodosylbenzene(salen)iron(iii) species has been
identified as the active intermediate by
EPR and NMR spectroscopy. R = aryl,
R’ = alkyl.
5228 – 5230
Evidence for the Formation of an Iodosylbenzene(salen)iron Active Intermediate in
a (Salen)iron(iii)-Catalyzed Asymmetric
Sulfide Oxidation
Mesoporous Materials
Y. Sakamoto, T.-W. Kim, R. Ryoo,
O. Terasaki*
5231 – 5234
Three-Dimensional Structure of LargePore Mesoporous Cubic Ia3̄d Silica with
Complementary Pores and Its Carbon
Replica by Electron Crystallography
Liquid Crystals
N. Gimeno, M. B. Ros,* J. L. Serrano,*
M. R. de la Fuente
5235 – 5238
Hydrogen-Bonded Banana Liquid Crystals
5112
A bicontinuous cubic structure was
revealed by electron crystallography on a
large-pore mesoporous silica with a cubic
Ia3̄d symmetry synthesized by using a
triblock copolymer as a structure-directing
agent. Its reconstructed structure (picture, left) is composed of an enantiomeric
pair of interwoven three-dimensional
mesoporous networks. Ordered complementary pores form interconnections
between the two main channel systems at
a special flat point of the G-surface (right).
Top banana! Hydrogen-bonded bent
complexes of benzoic acids (H donor)
and nonmesomorphic V-shaped 4’-stilbazoles (H acceptor) give rise to polar
smectic C (SmCP, see graphic) mesophases. The multifunctional character of
these noncovalent materials is confirmed
through their electrooptical, dielectric,
and luminescent responses.
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 5106 – 5115
Angewandte
Chemie
Solution-phase synthesis of single-crystal
ZnO disks and rings was achieved in high
yield at low temperature (70–90 8C) by
using an anionic surfactant as a template.
The reaction can be controlled by means
of the growth temperature and the molar
ratio of reagents to favor formation of
disks or rings. A growth mechanism is
proposed on the basis of structural
information provided by SEM and TEM.
ZnO Nanostructures
Genetic vaccination and gene therapy
research could benefit from the application of carbon nanotubes. Functionalized,
positively charged, water-soluble carbon
nanotubes are able to penetrate into cells
(see figure) and can transport plasmid
DNA by formation of noncovalent DNA–
nanotube complexes. Such nanotubes can
be used as novel nonviral delivery systems
for gene transfer.
Gene Technology
F. Li,* Y. Ding, P. Gao, X. Xin,
Z. L. Wang*
5238 – 5242
Single-Crystal Hexagonal Disks and Rings
of ZnO: Low-Temperature, Large-Scale
Synthesis and Growth Mechanism
D. Pantarotto, R. Singh, D. McCarthy,
M. Erhardt, J.-P. Briand, M. Prato,*
K. Kostarelos,* A. Bianco* 5242 – 5246
Functionalized Carbon Nanotubes for
Plasmid DNA Gene Delivery
One-dimensional supramolecular assembly of dendrimers (see picture) has been
achieved by multiple weak interactions
between highly branched molecules with
irregular structures. This finding contradicts the widely accepted assumption that
precise matching of directional interactions and steric constraints is required to
facilitate long-range one-dimensional
supramolecular assembly.
Self-Assembly of Dendrimers
M. Ornatska, K. N. Bergman, B. Rybak,
S. Peleshanko,
V. V. Tsukruk*
5246 – 5249
Nanofibers from Functionalized Dendritic
Molecules
Radical Chemistry
T. Usuki, T. Mita, M. J. Lear,* P. Das,
F. Yoshimura, M. Inoue, M. Hirama,*
K. Akiyama,* S. Tero-Kubota 5249 – 5253
A new spin on things? Spin trapping of
13
C-labeled bicyclic mimics of natural
nine-membered enediynes provided persuasive evidence for the spontaneous
Angew. Chem. Int. Ed. 2004, 43, 5106 – 5115
thermal generation of biradicals 1 and the
differential reactivity of the resulting C3
and C6 radical centers (see scheme; ST
spin trap; TBS tert-butyldimethylsilyl).
www.angewandte.org
Spin Trapping of 13C-Labeled p-Benzynes
Generated by Masamune–Bergman
Cyclization of Bicyclic Nine-Membered
Enediynes
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5113
Contents
Homogeneous Catalysis
M. K. Tse, C. DMbler, S. Bhor, M. Klawonn,
W. M[gerlein, H. Hugl,
M. Beller*
5255 – 5260
Development of a Ruthenium-Catalyzed
Asymmetric Epoxidation Procedure with
Hydrogen Peroxide as the Oxidant
Novel pyboxazines and the known pybox
ligands are used in the ruthenium-catalyzed asymmetric epoxidation of olefins
with H2O2 (see scheme). This new cata-
Solid-State Structures
lytic system is successful in the conversion of differently substituted aromatic
olefins and gives ee values of up to 84 %.
T time: The new binary antimonide Hf5Sb9
forms a unique variant of a square-planar
net, namely an unprecedented yet simple
T-shaped net (see picture, green) formed
by antimony atoms (red). The electronic
structure and bonding in the solid state
are analyzed by theoretical methods.
A. Assoud, K. M. Kleinke, N. Soheilnia,
H. Kleinke*
5260 – 5262
T-Shaped Nets of Antimony Atoms in the
Binary Antimonide Hf5Sb9
Host–Guest Chemistry
G. W. V. Cave, J. Antesberger, L. J. Barbour,
R. M. McKinlay,
J. L. Atwood*
5263 – 5266
Inner Core Structure Responds to
Communication between Nanocapsule
Walls
The facile self-assembly of six pyrogallol[4]arene molecules leads to a globular
truncated octahedron, which encapsulates a guest cluster consisting of ethyl
Molecular Switches
acetate and water molecules (see
scheme). The interactions between host
capsules can be controlled by derivatization of the exterior surface of the capsule.
All change: Three different output signals,
chromic, nonlinear optical, and magnetic,
can be altered simultaneously with the
molecular switch based on radical 1. The
electrochemical reduction and oxidation
of 1 is completely reversible. These redox
cycles can be repeated several times, and
the corresponding changes in the optical
properties can be monitored by visible
spectroscopy.
C. Sporer, I. Ratera, D. Ruiz-Molina,
Y. Zhao, J. Vidal-Gancedo, K. Wurst,
P. Jaitner, K. Clays, A. Persoons, C. Rovira,
J. Veciana*
5266 – 5268
A Molecular Multiproperty Switching
Array Based on the Redox Behavior of a
Ferrocenyl Polychlorotriphenylmethyl
Radical
Communications labeled with this symbol have been judged by two referees as being “very important papers”.
5114
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 5106 – 5115
Angewandte
Chemie
Service
Keywords
5270
Authors
5271
Preview
5273
Corrigendum
*
In this Communication, the temperature assignments on the right-hand side of Figure 4
were incorrect. The Editorial Office apologises for this error. The correct figure is shown.
Artificial Cells: Temperature-Dependent,
Reversible Li+-Ion Uptake/Release
Equilibrium at Metal Oxide
Nanocontainer Pores**
A. MNller,* D. Rehder,* E. T. K. Haupt,
A. Merca, H. BMgge, M. Schmidtmann,
G. Heinze-BrNckner
4466–4470
Angew. Chem. Int. Ed. 2004, 43
DOI 10.1002/anie.200453762
Angew. Chem. Int. Ed. 2004, 43, 5106 – 5115
www.angewandte.org
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5115
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