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Graphical Abstract Angew. Chem. Int. Ed. 452004

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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.
A. Glttli, W. F. van Gunsteren*:
Are NMR-Derived Model Structures for b-Peptides Representative for the Ensemble of Structures Adopted in Solution?
DOI: 10.1002/anie.200460384
Published online: November 2, 2004
T. Yamaguchi, T. Kimura, H. Matsuda, T. Aida*:
Macroscopic Spinning Chirality Memorized in Spin-Coated Films
of Spatially Designed Dendritic Zinc Porphyrin J-Aggregates
DOI: 10.1002/anie.200461431
Published online: November 11, 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.
Web Sites
A Crystallographic Database for Minerals
D. Hoppe and M. Ruck
6024
Hydrocarbon Thermal Isomerizations
Joseph J. Gajewski
reviewed by H. Hopf
6025
The Molecular World?Alkenes and
Aromatics
Peter Taylor, Michael Gagan
reviewed by H. Hopf
6025
http://www.geo.arizona.edu/AMS/
Books
Highlights
Cluster Chemistry
Six of one and half a dozen of the other: A
late-transition-metal octahedral cluster
[Rh6(PiPr3)6(m-H)12]2+ (1) with six phosphine ligands has been reported with a
structure and electron count akin to that
of early-transition-metal halide clusters,
and provides a unique link between the
two classes of cluster (see scheme).
Cluster 1 is also decorated with 12 hydride
ligands.
P. J. Dyson,* J. S. McIndoe* 6028 ? 6030
An Octahedral Rhodium Cluster with
Six Phosphine and 12 Hydride Ligands
and 10 Too Few Electrons
Minireviews
Reaction Specificity of Enzymes
U. T. Bornscheuer,*
R. J. Kazlauskas*
6032 ? 6040
Catalytic Promiscuity in Biocatalysis:
Using Old Enzymes to Form New Bonds
and Follow New Pathways
6012
Unfaithful enzymes, that is, enzymes that
catalyze alternative reactions, play a natural role in evolution and occasionally in
the biosynthesis of secondary metabolites. In one example pyruvate decarboxy-
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
lase catalyzes not only the natural reaction
(A) but also the enantioselective acyloin
condensation of acetaldehyde and benzaldehyde (B).
Angew. Chem. Int. Ed. 2004, 43, 6012 ? 6021
Angewandte
Chemie
Reviews
Nanobiotechnology
Blue-sky research bears down-to-earth
applications: this describes the integration of biological materials with nanomaterials to yield systems that can be applied
as biosensors or as building blocks for
electronic circuitry. This review describes
recent advances in the preparation and
the applications of biomolecule?nanoparticle conjugates. The picture shows
one such example with the magnetomechanical analysis of DNA.
E. Katz, I. Willner*
6042 ? 6108
Integrated Nanoparticle?Biomolecule
Hybrid Systems: Synthesis, Properties,
and Applications
Communications
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Meacham Ave., Elmont, NY 11003. Periodicals
Angew. Chem. Int. Ed. 2004, 43, 6012 ? 6021
Biocompatible nanotubes: Glycosylated
polymers designed to mimic natural
mucins were assembled on carbon nanotubes (see picture). Carbon nanotubes
coated with mucin mimics were soluble in
water, resisted nonspecific protein binding, and bound specifically to biomolecules through receptor?ligand interactions.
Biomimetic Synthesis
The dynamics of reversible photoinduced
electron transfer in individual perylenediimide?triphenylamine-based donor?
acceptor dendrimers immobilized in
polystyrene were investigated by singlemolecule spectroscopy. By changing the
local concentration of oxygen, it was
possible to influence the transition of the
charge-separation state (CSS) either to
the locally excited state (LES) or to the
ground state (GS, see graphic).
Single-Molecule Studies
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www.angewandte.org
X. Chen, G. S. Lee, A. Zettl,*
C. R. Bertozzi*
6111 ? 6116
Biomimetic Engineering of Carbon Nanotubes by Using Cell Surface Mucin Mimics
M. Cotlet, S. Masuo, M. Lor, E. Fron,
M. Van der Auweraer, K. MFllen,
J. Hofkens,* F. De Schryver* 6116 ? 6120
Probing the Influence of O2 on Photoinduced Reversible Electron Transfer in
Perylenediimide?Triphenylamine-Based
Dendrimers by Single-Molecule Spectroscopy
national chemical society, or whose institution
already subscribes, or who are retired or selfemployed consultants, print only: US$ 394.00.
Postage and handling charges included. All
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2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6013
Angewandte
Chemie
Coordination Polymers
A subtle electronic balance between
covalent and dative interactions involving
coordinated phosphanyl iminolate ligands
results in the formation of an oriented, 1 D
coordination/organometallic heterodimetallic polymer with Pd?Ag interactions
(shown as purple and green, respectively).
In the solid-state, the lipophilic aromatic
rings of the infinite zigzag chains are all
on one side of the planes of metal ions,
which results in an unusual layered
structure.
P. Braunstein,* C. Frison,
N. Oberbeckmann-Winter, X. Morise,
A. Messaoudi, M. BMnard, M.-M. Rohmer,
R. Welter
6120 ? 6125
An Oriented 1D Coordination/Organometallic Dimetallic Molecular Wire with
Ag Pd Metal?Metal Bonds
Amine Synthesis
T. Hayashi,* M. Kawai,
N. Tokunaga
A rational tuning of the arene sulfonamide
moiety (by introducing isopropyl groups
onto the phenyl ring) brought about high
enantioselectivity in the asymmetric
synthesis of diarylmethyl amines by the
title reaction (see scheme). Ar1 = 4CF3C6H4, 4-ClC6H4, 4-FC6H4, 3-MeOC6H4,
4-MeOC6H4, 2-MeC6H4, 1-naphthyl, Ph;
Ar2 = Ph, 4-FC6H4, 3-MeOC6H4, 4MeOC6H4.
Asymmetric Synthesis of Diarylmethyl
Amines by Rhodium-Catalyzed
Asymmetric Addition of Aryl Titanium
Reagents to Imines
Heterometallic Clusters
A triangular arrangement of gold atoms is
observed in the complex [Au3(mGaI2)3(Cp*Ga)5], which results when a
mixture of Cp*Ga and GaI3 capture the
reduced Au fragments from [LAuX]
(L = ligand, X = halide). The Au atoms are
bonded only to Ga atoms and each other:
two Au atoms are coordinated by two
Cp*Ga units and one Au atom is coordinated by a single Cp*Ga unit.
U. Anandhi, P. R. Sharp*
6128 ? 6131
A Gallium-Coated Gold Cluster
Ringing the changes: Complexes of azamacrocycles were used for the template
synthesis of extraordinary new cyclic and
acyclic chromium?nickel chains, which
include the ?S?-shaped cluster shown (see
picture) obtained when a cyclen-based
template is used. The results suggest a
new method for making sophisticated
polymetallic architectures.
Angew. Chem. Int. Ed. 2004, 43, 6012 ? 6021
6125 ? 6128
www.angewandte.org
Heterometallic Complexes
S. L. Heath, R. H. Laye, C. A. Muryn,
N. Lima, R. Sessoli,* R. Shaw,
S. J. Teat, G. A. Timco,*
R. E. P. Winpenny*
6132 ? 6135
Templating Open- and Closed-Chain
Structures around Metal Complexes of
Macrocycles
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6015
Contents
Photo-Switching
R. Mikami, M. Taguchi, K. Yamada,
K. Suzuki, O. Sato,
Y. Einaga*
6135 ? 6139
Reversible Photo-Switching of the
Magnetization of Iron Oxide
Nanoparticles at Room Temperature
In the solid state at room temperature,
reversible control of magnetic properties
was achieved with photo-illumination of a
composite material made up of g-Fe2O3
Carbon Nanotubes
nanoparticles encapsulated with n-octylamine and an azobenzene-containing
amphiphilic compound (see picture).
Mind the step! Single-wall carbon nanotubes grow along the atomic steps of
vicinal a-Al2O3 surfaces to give highly
aligned arrays of nanometer-wide wires on
a dielectric material. The nanotubes (see
blue background image) reproduce the
atomic features of the surface including
steps, facets, and kinks (see model). The
direction and morphology of the atomic
steps can be controlled by the crystal
miscut.
A. Ismach, L. Segev, E. Wachtel,
E. Joselevich*
6140 ? 6143
Atomic-Step-Templated Formation of
Single Wall Carbon Nanotube Patterns
Pd-Catalyzed Cyclizations
H. Zhang, E. M. Ferreira,
B. M. Stoltz*
6144 ? 6148
Direct Oxidative Heck Cyclizations: Intramolecular Fujiwara?Moritani Arylations
for the Synthesis of Functionalized
Benzofurans and Dihydrobenzofurans
No extra functionalization step is required
for palladium(ii)-catalyzed oxidative carbocyclizations like that shown, which
provide highly substituted benzofuran
and dihydrobenzofuran derivatives by net
The binding of a guest (metal ion, M+) to a
single host molecule (peptide) was studied by the measurement of the conductance of the peptide (see picture). The
conductance of the peptide in the metal?
peptide complexes increases by an
amount that is dependent on the
sequence and the length of the host.
Single-Molecule Conductance
X. Y. Xiao, B. Q. Xu,
N. J. Tao*
6148 ? 6152
Changes in the Conductance of Single
Peptide Molecules upon Metal-Ion
Binding
6016
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
dehydrogenation. The mechanism is
similar to that of Heck cyclizations. Products containing quaternary carbon stereocenters can be obtained in diastereomerically pure form.
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 6012 ? 6021
Angewandte
Chemie
Manganese magnets: Trimethylammonio
groups appended to the surface of a Mn12
single-molecule magnet lead to a highly
charged magnetic cluster that behaves as
an electron reservoir. This cluster spontaneously forms its two-electron reduced
species which has a ground spin state
S = 11. The cluster is a precursor for the
synthesis of network materials containing
Mn12 and for their deposition onto metal
and metal oxide surfaces.
It takes two: The complementary sulfate
and guanidinium ions in [C(NH2)3]
[N(CH3)4][SO4] both act as 3-connecting
nodes to give a 3D hydrogen-bonded
network with the chiral (10,3)-a topology
(see X-ray crystal structure; O red, S
yellow, H pink, N blue, C black). In
contrast, the 3-connected hydrogenbonded network in the much-studied
guanidinium sulfonates is 2D.
Magnetic Clusters
E. Coronado,* A. Forment-Aliaga,
A. Gaita-AriQo, C. GimMnez-Saiz,
F. M. Romero,*
W. Wernsdorfer
6152 ? 6156
Polycationic Mn12 Single-Molecule
Magnets as Electron Reservoirs with
S > 10 Ground States
Crystal Engineering
B. F. Abrahams, M. G. Haywood,
T. A. Hudson, R. Robson*
6157 ? 6160
Cubic, Hydrogen-Bonded (10,3)-a Networks in the Family [C(NH2)3][N(CH3)4]
[XO4] (X = S, Cr, and Mo)
Olefin Metathesis
P. E. Romero, W. E. Piers,*
R. McDonald
6161 ? 6165
Rapidly Initiating Ruthenium OlefinMetathesis Catalysts
Vacancies: Protonation of the ruthenium
carbide compounds [Cl2(L)(PR3)RuCD]
gives the 14-electron four-coordinate
ruthenium phosphonium alkylidenes
[Cl2(L)Ru=CH(PR3)]+[B(X)4] (see
scheme). These compounds which
already have a vacant coordination site
provide direct access to the active species
in olefin metathesis catalysis and thus
very fast initiation.
Nanoparticles and Catalysis
Particularly effective: The self-assembly of
triazacyclonane-functionalized thiols on
the surface of nanosize gold particles
provides a facile entry to functional gold
nanoparticles that, upon complexation
with ZnII, turn into powerful catalysts for
the cleavage of phosphate esters (see
scheme). Because of their RNase-like
behavior they are dubbed nanozymes.
Angew. Chem. Int. Ed. 2004, 43, 6012 ? 6021
F. Manea, F. B. Houillon, L. Pasquato,*
P. Scrimin*
6165 ? 6169
Nanozymes: Gold-Nanoparticle-Based
Transphosphorylation Catalysts
www.angewandte.org
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6017
Contents
Nanostructures
D. Wang, H. Luo, R. Kou, M. P. Gil, S. Xiao,
V. O. Golub, Z. Yang,* C. J. Brinker,
Y. Lu*
6169 ? 6173
A General Route to Macroscopic
Hierarchical 3D Nanowire Networks
Catalysis Methods
A. Pasc-Banu, C. Sugisaki, T. Gharsa,
J.-D. Marty, I. Gascon, G. Pozzi,
S. Quici, I. Rico-Lattes,
C. Mingotaud*
6174 ? 6177
A Catalytic Langmuir Film as a Model
for Heterogeneous and Homogeneous
Catalytic Processes
Pulling the rug out! A templated electrodeposition technique has been applied to
prepare stable 3D, organized networks of
metal or semiconductor nanowires (see
scheme). The process involves a) the
deposition of mesoporous silica onto an
electrode, b) the introduction of metals or
semiconductors into the pore channels,
and c) removal of the silica template to
yield the nanowire network.
An amphiphilic manganese salen complex
forms Langmuir films that catalyze the
epoxidation of cinnamyl alcohol with the
urea/hydrogen peroxide complex (UHP)
dissolved in the subphase (see picture).
Compression of the monolayer changes
the organization of the film and thus
strongly modifies the rate of the reaction,
which is enhanced for molecular areas of
about 140?160 R2.
Oxygen Heterocycles
S. H. Kang,* M. Kim,
S. Y. Kang
6177 ? 6180
Catalytic Asymmetric Mercuriocyclization
of g-Hydroxy-cis-Alkenes
2-Monosubstituted tetrahydrofurans 2 are
obtained with 73?95 % ee through the
catalytic enantioselective mercuriocyclization of g-hydroxy-(Z)-alkenes 1 by using
Hg(OAc)2 in the presence of HgII com-
plexed with tartrate-derived 4-(2-naphthyl)bisoxazoline 3. The chiral complex
was prepared from Hg(tfa)2 (0.2 equiv)
and 3 (0.3 equiv). The amount of MeOH
greatly influences the enantioselectivity.
Essential additives: The addition of
bis(1,3-butadienyl) compounds (tetraenes) was essential in the efficient Nicatalyzed cross-coupling of organozinc
reagents with alkyl bromides and a tosy-
late (see scheme, X = C(CO2Me)2 or
NCH2Ph). The efficiency of the Ni-catalyzed cross-coupling of an alkyl fluoride
with a Grignard reagent was also
improved by using these tetraenes.
Synthetic Methods
J. Terao, H. Todo, H. Watanabe, A. Ikumi,
N. Kambe*
6180 ? 6182
Nickel-Catalyzed Cross-Coupling Reaction
of Alkyl Halides with Organozinc and
Grignard Reagents with 1,3,8,10-Tetraenes
as Additives
6018
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2004, 43, 6012 ? 6021
Angewandte
Chemie
A simple and highly efficient method for
the Friedel?Crafts alkenylation of aromatic
compounds has been developed by using
a metal triflate (OTf) catalyst in an ionic
liquid (see scheme, bmim = 1-butyl-3methylimidazolium). Not only is the catalytic activity significantly enhanced in the
ionic liquid and by-product formation
decreased, but some reactions that were
not possible in conventional organic solvents were shown to proceed smoothly.
Synthetic Methods
Latex: Nitroxide-mediated emulsion polymerizations of n-butyl acrylate and styrene
were successfully carried out in a multistep process, with a novel water-soluble
SG1-based alkoxyamine as initiator. Fast
reactions lead to stable latex particles
containing polymers with controlled
molar masses.
Polymerizations
Pieces of eight: The reaction of [LAlI] with
elemental sulfur yields the crown shaped
complex [LAl(m-S3)2AlL] (L = HC(CMeNAr)2, Ar = 2,6-iPr2C6H3) containing an
Al2S6 eight-membered ring, in which two
(m-S3) chains are bridging two aluminum
atoms (see structure). The relative stabilities of the possible [L2Al2Sn] (n = 2?8)
species are estimated by theoretical calculation.
Dramatic Enhancement of Catalytic
Activity in an Ionic Liquid: Highly Practical
Friedel?Crafts Alkenylation of Arenes
with Alkynes Catalyzed by Metal Triflates
J. Nicolas, B. Charleux,* O. Guerret,
S. Magnet
6186 ? 6189
Nitroxide-Mediated Controlled Free-Radical Emulsion Polymerization of Styrene
and n-Butyl Acrylate with a Water-Soluble
Alkoxyamine as Initiator
Metal Polysulfides
Y. Peng, H. Fan, V. Jancik, H. W. Roesky,*
R. Herbst-Irmer
6190 ? 6192
[LAl(m-S3)2AlL]: A Homobimetallic
Derivative of the Sulfur Crown S8
Sulfur bridges: The reactions of [LAl(SH)2]
(L = HC(CMeNAr)2, Ar = 2,6-iPr2C6H3)
with LiN(SiMe3)2 in molar ratio 1:2 and
1:1, respectively, lead to species with the
formula [{LAl[(SLi)2(thf)3]}2]�THF and
[{LAl(SH)[SLi(thf)2]}2] in high yields.
These lithium salts react further with
[Cp2MCl2] (M = Ti, Zr; Cp = C5H5) to give
unique heterobimetallic sulfides of composition [LAl(m-S)2MCp2] (see structure;
M = Ti).
Angew. Chem. Int. Ed. 2004, 43, 6012 ? 6021
C. E. Song,* D.-u. Jung, S. Y. Choung,
E. J. Roh, S.-g. Lee*
6183 ? 6185
www.angewandte.org
Mixed-Metal Compounds
V. Jancik, H. W. Roesky,* D. Neculai,
A. M. Neculai,
R. Herbst-Irmer
6192 ? 6196
Preparation of [LAl(m-S)2MCp2] (M = Ti,
Zr) from the Structurally Characterized
Lithium Complexes [{LAl(SH)[SLi(thf)2]}2]
and [{LAl[(SLi)2(thf)3]}2]�THF
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6019
Contents
Phospholes
T. Baumgartner,* T. Neumann,
B. Wirges
6197 ? 6201
The Dithieno[3,2-b:2?,3?-d]phosphole
System: A Novel Building Block for Highly
Luminescent p-Conjugated Materials
Like a bolt from the blue, the blue
photoluminescence of novel phospholebased materials is extraordinarily intense.
The optoelectronic properties show great
stability and broad flexibility with respect
to wavelength, intensity, and tuneability.
The special features of the dithienophosphole system were incorporated in a
high-molecular-weight smart polymer
potentially suitable for optoelectronic
applications.
Feats of lead: The cluster compounds
[Pb12Hyp6] (1; see structure) and
[Pb10Hyp6] (2) result from the reaction of
the plumbylene [Pb{Si(SiMe3)3}2]
([PbHyp2]) with hydride sources, such as
PH3 or [{(Ph3P)CuH}6]. They are the first
examples of neutral lead clusters bearing
s-bonded substituents. Whereas 2 is isolated from the reaction mixture on a
multigram scale, 1 is only obtained in
traces.
Cluster Compounds
K. W. Klinkhammer,* Y. Xiong,
S. Yao
6202 ? 6204
Molecular Lead Clusters?From Unexpected Discovery to Rational Synthesis
Organocatalysis
C. Burstein, F. Glorius*
6205 ? 6208
Organocatalyzed Conjugate Umpolung of
a,b-Unsaturated Aldehydes for the
Synthesis of g-Butyrolactones
Metallocenes
H. Schumann,* S. Schutte, H.-J. Kroth,
D. Lentz*
6208 ? 6211
Butenyl-Substituted Alkaline-Earth
Metallocenes: A First Step towards Olefin
Complexes of the Alkaline-Earth Metals
Advantage organocatalysis: N-heterocyclic carbenes can generate homoenolate
equivalents under mild conditions by
conjugate umpolung of a,b-unsaturated
aldehydes. This organocatalytic reaction
allows an efficient one-step synthesis of
substituted g-butyrolactones 1 (see
scheme, Mes = mesityl).
Sandwich any one? The bis(butenyltetramethylcyclopentadienyl) complexes of
calcium (2), strontium and barium exhibit
an interaction of the alkaline-earth metals
with olefin double bonds. Whereas the
magnesium derivative (1) crystallizes as a
sandwich complex with coplanar cyclopentadienyl ligands and free butenyl side
chains, these coordinate to the metal in
the analogous but open sandwich complexes of the larger metals calcium,
strontium, and barium.
Communications labeled with this symbol have been judged by two referees as being ?very important papers?.
The issues for November 2004 appeared online on the following dates
Issue 41: October 13. � Issue 42: October 20. � Issue 43: November 2. � Issue 44: November 11
6020
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 6012 ? 6021
Angewandte
Chemie
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