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Graphical Abstract Angew. Chem. Int. Ed. 262006

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The following Communications have been judged by at least two referees to be “very
important papers” and will be published online at soon:
A. Narayanaswamy, H. Xu, N. Pradhan, X. Peng*
Single-Crystal Nanoflowers with Different Chemical
Compositions and Physical Properties Grown by Limited
Ligand Protection
J. L. Alonso,* E. Cocinero, A. Lesarri, M. E. Sanz, J. L$pez
The Glycine–Water Complex
A. Tao, P. Sinsermsuksakul, P. Yang*
Polyhedral Silver Nanocrystals with Distinct Scattering
J. van Bokhoven*, C. Louis, J. Miller, M. Tromp, O. Safonova,
P. Glatzel
Activation of Oxygen on Gold–Alumina Catalysts: In Situ
High-Energy Resolution Fluorescence and Time-Resolved X-ray
Chemistry of Peptide Synthesis
N. Leo Benoiton
Candid Science IV
Magdolna Hargittai, Istvn Hargittai
reviewed by S. Kent
reviewed by G. B. Kauffman
Catalyst Design
B. Voit*
4238 – 4240
Sequential One-Pot Reactions Using the
Concept of “Site Isolation”
Acidic and basic sites can be isolated by
incorporation in the core of star-shaped
polymers (see picture). Fr6chet, Hawker,
and co-workers have used these polymerbased catalysts for homogeneous-phase
one-pot multistep reactions. Similarly,
Kaneda et al. have demonstrated the siteisolation concept in heterogeneous systems by use of different types of layered
Low-Coordinate Compounds
M. Weidenbruch*
4241 – 4242
A Stable Silylenoid and a Donor-Stabilized
Chlorosilylene: Low-Coordinate Silicon
Compounds—A Never-Ending Story?
And so on: The silylenoid 1 and the
stabilized chlorosilylene 2 represent new
types of low-coordinate silicon compounds, which, on account of the pre-
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
sence of a silicon–halogen bond in each,
should form the basis of interesting
subsequent chemistry.
Angew. Chem. Int. Ed. 2006, 45, 4222 – 4231
Amorphous Compounds
Teaming up for results: The structure of
the amorphous ceramic Si3B3N7 has been
investigated by combining experimental
data with computer simulations. Of the
many structural models generated (see
picture for an example; Si red, B blue,
N green), those that consider the actual
synthesis route of the material agree most
closely with the experimental results.
M. Jansen,* J. C. Sch<n,
L. van W=llen
4244 – 4263
The Route to the Structure Determination
of Amorphous Solids: A Case Study of the
Ceramic Si3B3N7
Good organizational skills: Evidence for
the formation of Pt clusters during classical microemulsion synthesis was
obtained by scanning tunneling microscopy. The Pt clusters were spontaneously
assembled on an Au(111) surface to form
high-aspect-ratio objects. 2D nanoislands
form and subsequently self-assemble in
parallel rows of several hundreds of
nanometers in length.
A curved retinal: Difference electron-density data between the photoreceptor protein rhodopsin and its primary photoreaction intermediate bathorhodopsin
have provided a crystallographic model
for the cis–trans isomerization of the
chromophore retinal therein during the
primary process in dim-light vision (see
picture; the curved polyene structure of
retinal in bathorhodopsin is shown in red,
while that in rhodopsin is colored green).
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Angew. Chem. Int. Ed. 2006, 45, 4222 – 4231
O. Guill6n-Villafuerte, G. GarcAa, B. Anula,
E. Pastor, M. C. Blanco,
M. A. LBpez-Quintela,
A. Hernndez-Creus,
G. A. Planes*
4266 – 4269
Assembly of Subnanometric 2D Pt
Nanoislands in Parallel Rows onto
Au(111) by Self-Organization of Pt
Chemistry of Vision (1)
H. Nakamichi, T. Okada*
4270 – 4273
Crystallographic Analysis of Primary
Visual Photochemistry
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2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chemistry of Vision (2)
Seeing double: Quantum-mechanical
refinement of the X-ray crystal structure of
bathorhodopsin (see picture; before optimization green; optimized structure red)
highlights the twisted geometry of the
chromophore. Calculated Raman, UV/Vis,
and CD spectral properties of this first
intermediate of the rhodopsin visual cycle
agree with those observed experimentally.
M. Schreiber, M. Sugihara, T. Okada,
V. Buss*
4274 – 4277
Quantum Mechanical Studies on the
Crystallographic Model of
Peptide Receptors
C. Schmuck,* P. Wich
All in a row: The screening of a combinatorial library with 320 substrates shows
that an artificial triscationic receptor efficiently binds anionic tetrapeptides in
water with association constants up to
Ka = 27 000 m1. Moreover, the receptor
shows a remarkable sequence-dependent
stereoselectivity between d-Ala and l-Ala
in certain positions of the tetrapeptide.
4277 – 4281
Sequence-Dependent Stereoselectivity in
the Binding of Tetrapeptides in Water by a
Flexible Artificial Receptor
Supramolecular Chemistry
H. Kawai,* T. Umehara, K. Fujiwara,
T. Tsuji,* T. Suzuki
4281 – 4286
Building bridges: Imine bridges between
the axle and ring components in rotaxanes
allow simple rotaxane synthesis and a
novel method for motion control to be
developed. The submolecular mobility in
this rotaxane-type assembly is regulated
by the imine-bond formation/cleavage
(see scheme). The relative abundance of
the [2]rotaxane increases with decreasing
temperature under dynamic equilibrium
Dynamic Covalently Bonded Rotaxanes
Cross-Linked by Imine Bonds between the
Axle and Ring: Inverse Temperature
Dependence of Subunit Mobility
Protein Modification
P.-C. Lin, S.-H. Ueng, M.-C. Tseng, J.-L. Ko,
K.-T. Huang, S.-C. Yu, A. K. Adak,
Y.-J. Chen, C.-C. Lin*
4286 – 4290
Out of site: A protein expression system
was combined with CuI-catalyzed 1,2,3triazole formation to modify a target
protein at its C terminus. The immobilized core protein can be modified by
diverse small molecules in a site-specific
Angew. Chem. Int. Ed. 2006, 45, 4222 – 4231
manner (see picture). Protein conjugation
with a diazido linker gives a homodimeric
protein, and microarrays can be fabricated
by site-specific covalent binding to functionalized surfaces.
Site-Specific Protein Modification through
Cui-Catalyzed 1,2,3-Triazole Formation
and Its Implementation in Protein
Microarray Fabrication
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Back and forth: Reaction of [RuCl2(PPh3)3], 1,3-bis(diphenylphosphino)propane, and an amido ligand yields the
coordination-driven self-assembly of two
ruthenamacrocycles through NH···ClRu,
p···p, and CH···p interactions (see picture; purple Ru, green Cl, orange P, red O,
blue N, gray C, white H). Reversible
dissociation/association behavior of this
complex in solution is controlled by halide
Y. J. Park, J.-S. Kim, K.-T. Youm, N.-K. Lee,
J. Ko,* H.-s. Park,*
M.-J. Jun*
4290 – 4294
A Self-Complementary Assembly of
Metallamacrocycles Directed by
RuCl···HN Hydrogen Bonds and
Its Reversible Dichotomy by Halide
Anions in Solution
Mesoporous Materials
C. Gao, Y. Sakamoto,* K. Sakamoto,
O. Terasaki, S. Che*
4295 – 4298
Synthesis and Characterization of
Mesoporous Silica AMS-10 with
Bicontinuous Cubic Pn3̄m Symmetry
S. Nagashima, M. Murata,
H. Nishihara*
4298 – 4301
A Ferrocenylspiropyran That Functions
as a Molecular Photomemory with
Controllable Depth
F. Wu, R. Hong, J. Khan, X. Liu,
L. Deng*
4301 – 4305
Asymmetric Synthesis of Chiral Aldehydes
by Conjugate Additions with Bifunctional
Organocatalysis by Cinchona Alkaloids
Woven into place: By precisely controlling
the neutralization degree of the anionic
surfactant template, mesoporous silica
with different structures was prepared,
such as AMS-10. Detailed characteriza-
tions of AMS-10 show that it is a novel
bicontinuous cubic Pn3̄m mesophase.
The mesostructure is composed of an
interwoven enantiomeric pair of 3D
networks (see picture).
Deep memory: A photochromic molecule
can control the stability of its merocyanine
(MC) form by changing the oxidation state
of the ferrocene (Fc) moiety (see picture).
This ferrocenyl–spiropyran (SP) system
works not only in solution but also in a
polymer electrolyte.
A highly efficient asymmetric conjugate
addition of carbonyl donors to a,b-unsaturated aldehydes is realized with 6’-OH
cinchona alkaloids as bifunctional organocatalysts. A wide range of a-substituted
b-ketoesters and a-substituted a-cyanoacetates can be employed as donors,
whereas acrolein and b-substituted a,bunsaturated aldehydes are suitable
acceptors for this enantioselective
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 4222 – 4231
S. Brandau, A. Landa, J. Franz6n,
M. Marigo, K. A. Jørgensen* 4305 – 4309
In addition: The scope of the title reaction
is demonstrated by the synthesis of chiral
lactones and lactams. The latter class of
compounds is very important for the
preparation of the pharmaceutical compounds such as ()-paroxetine and
Organocatalytic Conjugate Addition of
Malonates to a,b-Unsaturated Aldehydes:
Asymmetric Formal Synthesis of
()-Paroxetine, Chiral Lactams, and
Adding corners: A metallacarborane with
15 vertices was prepared by reduction of
14-vertex carborane 1 to nido-carborane
dianion 2 and subsequent reaction with
[{(p-cymene)RuCl2}2] to give 3 (see
scheme). The key to obtaining successively larger clusters is prevention of redox
reactions (such as that to give 4).
Cornering heteroboranes: The 15-vertex
heteroborane 1-(p-cymene)-8,14-m-(CH2)31,8,14-closo-RuC2B12H12 has been prepared
(see structure; B orange, Ru blue, C gray).
The RuC2B12 polyhedron has the form of a
pentacosahedron (24 triangular faces and
1 quadrilateral face). In solution at elevated temperatures the structure is in
tautomeric equilibrium by a “square–
diamond–square” rearrangement involving the quadrilateral face.
L. Deng, J. Zhang, H.-S. Chan,
Z. Xie*
4309 – 4313
Synthesis and Structure of 14- and
15-Vertex Ruthenacarboranes
R. D. McIntosh, D. Ellis, G. M. Rosair,
A. J. Welch*
4313 – 4316
A 15-Vertex Heteroborane
Natural Product Synthesis
A. Sabahi, A. Novikov,
J. D. Rainier*
Closing the ring: The cyclization of a 2thioindole with an electrophilic substituent serves as the key transformation in a
synthetic strategy for the generation of
Angew. Chem. Int. Ed. 2006, 45, 4222 – 4231
indole alkaloids of the perophoramidine
and communesin class. DBU = 1,8diazabicyclo[5.4.0]undec-7-ene, Ms =
methanesulfonyl chloride.
4317 – 4320
2-Thioindoles as Precursors to SpiroFused Indolines: Synthesis of
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
CO Bond Formation
C. H. Burgos, T. E. Barder, X. Huang,
S. L. Buchwald*
4321 – 4326
Significantly Improved Method for the PdCatalyzed Coupling of Phenols with Aryl
Halides: Understanding Ligand Effects
A variety of diaryl ethers were synthesized
by the Pd-catalyzed reaction of (hetero)aryl halides and phenols. These reactions
were achieved through the use of two new
Non-natural Base Pairs
di-tert-butylphosphino biaryl ligands that
overcome several limitations of previously
described methods.
Getting on with it: A common problem
with hydrophobic non-natural base
pairs—the inefficient extension following
such a base pair—is reduced by using the
methylpyridone scaffold, which simultaneously limits another frequent problem
of non-natural bases: mispairs with
A. M. Leconte, S. Matsuda, G. T. Hwang,
F. E. Romesberg*
4326 – 4329
Efforts towards Expansion of the Genetic
Alphabet: Pyridone and Methylpyridone
Chemical Genetics
S. M. Lamos, C. J. Krusemark, C. J. McGee,
M. Scalf, L. M. Smith,
P. J. Belshaw*
4329 – 4333
Mixed Isotope Photoaffinity Reagents for
Identification of Small-Molecule Targets
by Mass Spectrometry
Twin peaks: A facile and economic route
has been developed for the incorporation
of deuterated benzophenones (a widely
used photoaffinity tag) into probes.
Attachment of these mixed-isotope labels
Cluster Compounds
M. Brynda, R. Herber,* P. B. Hitchcock,
M. F. Lappert,* I. Nowik, P. P. Power,*
A. V. Protchenko, A. Růžička,
J. Steiner
4333 – 4337
Higher-Nuclearity Group 14 Metalloid
Clusters: [Sn9{Sn(NRR’)}6]
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
to the immunosuppressive drug CsA
facilitated the mass spectrometric identification of a target of CsA (see picture)
from a mixture of proteins.
A perfect tin! Two 15-nuclear tin metalloid
clusters [Sn15Z6] (Z = N(2,6-iPr2C6H3)(SiMe2X); X = Me, Ph), having an unprecedented body-centered metal core (see
picture; only N atoms of the amide
ligands shown), were prepared by reduction of the appropriate amidotin(II) chloride with KC8 or Li[BHsBu3]. M<ssbauer
spectra showed two distinct quadrupolesplitting sites in the ratio of 1.5:1 for the
Sn9 atoms and the six amido-bound tin
Angew. Chem. Int. Ed. 2006, 45, 4222 – 4231
An electronic chameleon: The planar
cyclogermylene 1 can be described by the
resonance structures 1 A and 1 B. It is
accessible in 79 % yield by dehydrohalogenation of the corresponding (b-diketiminato)chlorogermylene by LiN(SiMe3)2.
Although the contribution of the dipolar
resonance structure 1 A is relatively small,
its influence is seen in the transformations of 1 with Me3SiOTf or 1,2-dibromoethane. R = 2,6-diisopropylphenyl.
Angew. Chem. Int. Ed. 2006, 45, 4222 – 4231
Rungs of a ladder: A solvated linear 1D
coordination polymer [Ag(m-bpe)(H2O)](CF3CO2)·CH3CN (bpe = 4,4’-bipyridylethylene) with no parallel dispositions of
the double bonds in the crystal structure
undergoes photodimerization when desolvated. This finding is attributed to the
lateral movements of adjacent linear
strands on desolvation, which form a
ladderlike structure (see picture; Ag light
blue, C gray, N purple, O red).
Crystal Engineering
Radically stable: An extremely stable Pheterocyclic organic radical was isolated
after oxidation of a sterically encumbered
1,3-diphosphacyclobutenyl anion generated from Mes*CP (Mes* = 2,4,6tBu3C6H2). The structure of the 1,3diphosphacyclobuten-4-yl radical, as
determined by X-ray analysis, was comparable to data obtained from EPR analysis and a computational model.
Phosphorus Heterocycles
In control: A cyclization reaction of an
allylic b-imidazolinonyl-b-ketoester 1 is
carried out in a MnIII-promoted radical
cascade. The reaction pathway (5-exo/6endo or 5-exo/5-exo) can be directed to
construct the central cyclopentyl and
cyclohexenyl core skeletons (2 and 3) of
two classes of oroidin dimers with regiocontrol. An oxidative rearrangement can
also be used to convert 2 into 3.
PG = protecting group.
Cascade Reactions
M. Nagarathinam,
J. J. Vittal*
4337 – 4341
Anisotropic Movements of Coordination
Polymers upon Desolvation:
Solid-State Transformation of a Linear
1D Coordination Polymer to a
Ladderlike Structure
S. Ito,* M. Kikuchi, M. Yoshifuji,*
A. J. Arduengo, III, T. A. Konovalova,
L. D. Kispert
4341 – 4345
Preparation and Characterization of an
Air-Tolerant 1,3-Diphosphacyclobuten-4-yl
X. Tan, C. Chen*
4345 – 4348
Regiocontrol in MnIII-Mediated Oxidative
Heterobicyclizations: Access to the Core
Skeletons of Oroidin Dimers
Main-Group-Element Compounds
M. Driess,* S. Yao, M. Brym,
C. van W=llen
4349 – 4352
A Heterofulvene-Like Germylene with a
Betain Reactivity
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Borylene Complexes
H. Braunschweig,* C. Burschka,
M. Burzler, S. Metz,
K. Radacki
4352 – 4355
Molecular Structure and Cluster
Formation of a tert-Butylborylene Complex
B finds a new hive: The X-ray structure of
[m-BtBu{(h5-C5H5)Mn(CO)2}2] represents
the first crystallographic characterization
of an alkylborylene complex. Its substituted counterpart [m-BtBu{(h5-C5H4Me)Mn(CO)2}2] reacts cleanly with [Pd(PCy3)2]
(Cy = cyclohexyl) to form the first heterometallic m3-borylene complex 1, for which
DFT and ELF computations indicate a
localized bonding situation.
Microcontact Printing
D. Burdinski,* M. Saalmink,
J. P. W. G. van den Berg,
C. van der Marel
4355 – 4358
Universal Ink for Microcontact Printing
Hot off the press: A single mixed ink
composition comprising aliphatic thiol
and phosphonic acid inks has been used
for the soft lithographic patterning of
metal and metal oxide surfaces by micro-
An aluminating discovery: Hydroalumination of 1,4-di(tert-butyl)butadiyne with
di(tert-butyl)aluminum hydride affords a
persistent butadien-2-yl cation (red in
scheme). The stabilization of this compound is achieved in particular by hyperconjugation with an AlC bond, and the
effective chelating coordination by the
aluminum atoms prevents the migration
of the hydride ion to the electrophilic
cationic carbon atom.
W. Uhl,* J. Grunenberg, A. Hepp,
4358 – 4361
M. Matar, A. Vinogradov
Facile Formation of a Persistent
Butadien-2-yl Cation Stabilized by
Hyperconjugation with an AlC Bond
O. Kretschmann, S. W. Choi, M. Miyauchi,
I. Tomatsu, A. Harada,
H. Ritter*
4361 – 4365
Switchable Hydrogels Obtained by
Supramolecular Cross-Linking of
Adamantyl-Containing LCST Copolymers
with Cyclodextrin Dimers
contact printing and wet chemical etching. The method takes advantage of the
intrinsic selectivity of the ink transfer to
different substrate materials.
En route to intelligent hydrogels: Copolymers of N-isopropylacrylamide containing
adamantyl groups can be cross-linked
noncovalently with cyclodextrin dimers.
This results in thermosensitive hydrogels
with cloud points that are lower than
those of the pure copolymers. Addition of
monomeric methylated cyclodextrin
results in an increase in the cloud points
but has no significant influence on the
viscosity of the copolymer solution.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 4222 – 4231
Mistaken identity: The high-pressure
synthesis of PtN in the zinc blende
structure type is refuted on the basis of
first-principles electronic-structure
calculations, which demonstrate that this
low-density phase is energetically
unstable and cannot be produced at high
pressure. The denser cooperite structure
type is preferable for PtN (see picture;
NPt4 tetrahedra are yellow).
Solid-State Structures
Golden bridge: In the title complex, the
auride anion acts as an acceptor in
NH···Au hydrogen bonds (see molecular structure; C gray, H white, N blue,
O red, Au orange, Rb violet). For the first
time, experimental values for an H···Au
distance and the corresponding N-H-Au
angle could be determined.
Hydrogen Bonds
J. von Appen, M.-W. Lumey,
R. Dronskowski*
4365 – 4368
Mysterious Platinum Nitride
H. Nuss, M. Jansen*
4369 – 4371
[Rb([18]crown-6)(NH3)3]Au·NH3 : Gold as
Acceptor in NH···Au Hydrogen Bonds
Molecular Rotors
L. Wang, F. Hampel,
J. A. Gladysz*
4372 – 4375
“Giant” Gyroscope-Like Molecules
Consisting of Dipolar Cl-Rh-CO Rotators
Encased in Three-Spoke Stators That
Define 25–27-Membered Macrocycles
Yet another feat for the Grubbs catalyst:
Reactions with 1 a,b followed by hydrogenations give 2 a,b. The sizeable cavities of
2, which were characterized crystallographically, allow for rapid Cl-Rh-CO rotation
in solution. Reactions with ArCCLi give
ArCC–Rh–CO species; when the aryl
group is sufficiently large, it is confined
between two macrocycles, blocking
Sister Journals
Angew. Chem. Int. Ed. 2006, 45, 4222 – 4231
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4376 – 4377
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abstract, 262006, int, angel, chem, graphical
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