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Graphical Abstract Angew. Chem. Int. Ed. 382004

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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.
C. Serre,* F. Millange, S. Surbl, G. Frey:
A Route to the Synthesis of Trivalent
Transition-Metal Porous Carboxylates with
Trimeric Secondary Building Units
DOI: 10.1002/anie.200454250
Published online: September 7, 2004
C. Mellot-Draznieks,* J. Dutour, G. Frey:
Hybrid Organic–Inorganic Frameworks:
Routes for Computational Design and
Structure Prediction
DOI: 10.1002/anie.200454251
Published online: September 3, 2004
T. Shima, F. Hampel, J. A. Gladysz*:
Molecular Gyroscopes: {Fe(CO)3} and
{Fe(CO)2(NO)}+ Rotators Encased in
Three-Spoke Stators; Facile Assembly by
Alkene Metatheses
DOI: 10.1002/anie.200460534
Published online: August 27, 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.
Obituary
Colin Eaborn (1923–2004): Organosilicon Compounds
4978
J. D. Smith
Books
Basic Principles in Applied Catalysis
Computational Chemistry
Manfred Baerns
Errol G. Lewars
reviewed by X. Nijhuis,
B. Weckhuysen
4979
reviewed by R. Berger
4979
Highlights
Expansion-Free Materials
K. St+we*
4982 – 4984
YbGaGe: Zero Thermal Expansion as a
Result of an Electronic Valence Transition?
In contrast to classic ZTE materials
(ZTE = zero thermal expansion), the ZTE
effect in YbGaGe (see crystal structure) is
caused by the change in the valency of the
ytterbium ion from + 2.6 to + 2 with
decreasing temperature. This change in
the valence state compensates for the
contraction of the net as the temperature
decreases.
Electron Transfer
A. Harriman*
Shedding new light on the matter: Rather
than the conventional approach of utilizing the cascade effect, charge separation
can be stabilized in artificial photosynthetic systems simply by the geometry. In
these latter systems, light-induced charge
separation (CS) in a closely spaced
molecular dyad is followed by exceptionally slow charge recombination (CR, see
picture) to give a charge-separated state
with a lifetime of up to 120 s.
4985 – 4987
Unusually Slow Charge Recombination in
Molecular Dyads
4968
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2004, 43, 4968 – 4976
Angewandte
Chemie
Minireviews
Nanostructures
Crystalline nanoparticles can be prepared
at ambient temperatures in ionic
liquids—highly polar organic solvents
with a preorganized solvent structure. The
pronounced self-organization of the solvent is used in the synthesis of highly
organized hybrid nanostructures like the
lamellar silica shown in the picture.
M. Antonietti,* D. Kuang, B. Smarsly,
Y. Zhou
4988 – 4992
Ionic Liquids for the Convenient Synthesis
of Functional Nanoparticles and Other
Inorganic Nanostructures
Reviews
Polycyclic Arenes
From corannulene to C60 : Geodesic polyarenes can be synthesized in the laboratory by bending flat molecules and stitching them up into molecular bowls, baskets, and balls, using rational chemical
methods.
L. T. Scott*
4994 – 5007
Methods for the Chemical Synthesis of
Fullerenes
Communications
Luminescence
Red glow in daylight … chemist’s delight!
An efficient transfer of excitation energy
from the ligand to the luminescent states
of the coordinated EuIII ion in 1 occurs
from the singlet excited state of the ligand.
The complex shows characteristic bright
red Eu-centered emission with a quantum
yield of 0.52 when sensitized with visible
light.
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Meacham Ave., Elmont, NY 11003. Periodicals
Angew. Chem. Int. Ed. 2004, 43, 4968 – 4976
C. Yang, L.-M. Fu, Y. Wang,* J.-P. Zhang,*
W.-T. Wong,* X.-C. Ai, Y.-F. Qiao, B.-S. Zou,
L.-L. Gui
5010 – 5013
A Highly Luminescent Europium Complex
Showing Visible-Light-Sensitized Red
Emission: Direct Observation of the
Singlet Pathway
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2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4969
Angewandte
Chemie
Enantioselectivity Determination
R. Eelkema, R. A. van Delden,
B. L. Feringa*
5013 – 5016
Direct Visual Detection of the
Stereoselectivity of a Catalytic Reaction
Color vision: The enantiomeric excess of
the products of an enantioselective
catalytic reaction can be determined by
a liquid-crystal-based color test. After a
simple workup, doping of the reaction
product into a liquid crystal affords
brightly colored LC phases, with colors
depending on the enantiomeric excess of
the product (see picture).
Self-Assembly
Magic rings: The trick of kinetically controlled cross-catenation of two different
PdII-linked coordination rings (see picture) lies in the large difference in the
catenation rate of the two rings as a result
of steric hindrance of the ligands.
A. Hori, K. Yamashita,
M. Fujita*
5016 – 5019
Kinetic Self-Assembly: Selective CrossCatenation of Two Sterically Differentiated
PdII-Coordination Rings
Inclusion Compounds
Y. Miyahara,* K. Goto, M. Oka,
T. Inazu
5019 – 5022
Remarkably Facile Ring-Size Control in
Macrocyclization: Synthesis of Hemicucurbit[6]uril and Hemicucurbit[12]uril
A question of concentration: The condensation of ethyleneurea and formaldehyde can be controlled perfectly by the
HCl concentration to provide either a
hemicucurbit[6]uril 1, which functions as a
host, or hemicucurbit[12]uril 2, which acts
as a gelating agent, in yields of 94 and
93 %, respectively.
Three reversible reductions are observed
for a new cyclic tricubane cluster. In the
solid state, the cluster displays a large,
electron-rich pocket containing an encapsulated Et4N+ ion (see structure). These
characteristics might allow the use of this
cluster as a multielectron reducing agent.
Angew. Chem. Int. Ed. 2004, 43, 4968 – 4976
www.angewandte.org
Superclusters
M. Koutmos,
D. Coucouvanis*
5023 – 5025
Superclusters: A Host–Guest Complex
with a Cyclic Array of Three Bridged
MoFe3S4 Clusters
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4971
Contents
Bioinorganic Chemistry
S. Kunze, F. Zobi, P. Kurz, B. Spingler,
R. Alberto*
5025 – 5029
Vitamin B12 as a Ligand for Technetium
and Rhenium Complexes
Cluster Compounds
E. Goto, R. A. Begum, S. Zhan, T. Tanase,*
5029 – 5032
K. Tanigaki, K. Sakai
Linear, Redox-Active Pt6 and Pt2Pd2Pt2
Clusters
Robust complexes with a central {Co-CNRe(Tc)} feature are formed when the
cyanide ligand in vitamin B12 acts as
bridging ligand between rhenium and
technetium carbonyl complexes (see picture). This concept paves the way for
radiolabeling of vitamin B12 or metalmediated coupling of bioactive molecules.
A piece of jewelry is the complex [Pt4M2(mH)(m-dpmp)4(XylNC)2](PF6)3 (M = Pt, see
structure), which contains the longest
platinum chain characterized so far. This
complex and the related compound with
M = Pd are redox-active and can be readily
oxidized to the electron-deficient clusters
[Pt4M2(m-dpmp)4(XylNC)2](PF6)4 (M = Pt,
Pd) with dynamic structural changes in
the metal strings. Xyl = 2,6-dimethylphenyl, dpmp = bis(diphenylphosphanylmethyl)phenylphosphane.
Host–Guest Systems
D. N. Dybtsev, H. Chun,
K. Kim*
5033 – 5036
Rigid and Flexible: A Highly Porous
Metal–Organic Framework with Unusual
Guest-Dependent Dynamic Behavior
A large H2 sorption capacity and high
surface area are properties of the depicted
metal–organic porous material, which is
easily synthesized on a large scale from
readily available chemicals. The rigid
framework of [Zn2(1,4-bdc)2(dabco)]
Self-assembly
Noninterpenetrating structures are
formed by self-assembly of cadmium salts
and long flexible ligands. In one case
exceptional ninefold interlocked homochiral helices are built from achiral components (see picture). The helices are
chemically independent but physically
interwoven. This represents the highest
degree of entanglement presently known
for a noninterpenetrating system.
X.-L. Wang, C. Qin, E.-B. Wang,* L. Xu,
Z.-M. Su,* C.-W. Hu
5036 – 5040
Interlocked and Interdigitated Architectures from Self-Assembly of Long Flexible
Ligands and Cadmium Salts
4972
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
(1,4-H2bdc = 1,4-benzenedicarboxylic
acid; dabco = diazabicyclo[2.2.2]octane)
is also flexible enough to exhibit unusual
guest-dependent dynamic behavior, as
shown (DMF = N,N-dimethylformamide).
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Angew. Chem. Int. Ed. 2004, 43, 4968 – 4976
Angewandte
Chemie
Specific monomer sequences in aromatic
copolyimides are recognized through their
p-stacking and hydrogen-bonding interactions with a sterically and electronically
complementary molecular tweezer. These
interactions enable the tweezer molecule
to “read” monomer sequences comprising up to 27 aromatic rings by multiple
adjacent binding to neighboring sites on
the polymer chain (see picture).
H. M. Colquhoun,* Z. Zhu
5040 – 5045
Recognition of Polyimide Sequence
Information by a Molecular Tweezer
Diazadiene Ligands
A couple of surprises: The reactions of
[(C13H9)2Yb(thf)2] with diazadienes (2,6iPr2C6H3)N=CR CR=N(2,6-iPr2C6H3)
(R = H, Me) result in unexpected YbII
complexes, which arise either from the
coupling of the fluorene and the diazadiene ligands (when R = H, see picture) or
from C H bond activation of the diazadiene ligand (when R = Me).
A. A. Trifonov,* E. A. Fedorova, G. K. Fukin,
N. O. Druzhkov,
M. N. Bochkarev
5045 – 5048
C C Coupling and C H Bond
Activation—Unexpected Pathways in
the Reactions of [Yb(h5-C13H9)2(thf)2]
with Diazadienes
Made-to-measure nanobelts: Metastable
vanadium dioxide single-crystal nanobelts
(see picture) were prepared by a hydrothermal reduction method by treating an
ammonium metavanadate solution with
formic acid. The morphology of the belts
could be adjusted by varying the reaction
parameters, such as temperature, pH, and
reaction time.
Nanostructures
J. Liu, Q. Li, T. Wang, D. Yu,
Y. Li*
5048 – 5052
Metastable Vanadium Dioxide Nanobelts:
Hydrothermal Synthesis, Electrical Transport, and Magnetic Properties
Homogeneous Catalysis
Oxidative addition of a distannane to a
palladium(0) complex occurs during the
distannylation of in situ generated arynes
with distannanes in the presence of a
catalytic amount of a palladium/tert-octyl
isocyanide (tOcNC) complex to give 1,2distannylarenes in moderate to high yields
(see scheme). Bisarynes and cyclohexynes
can also be used as substrates for the
reaction.
Angew. Chem. Int. Ed. 2004, 43, 4968 – 4976
Molecular Recognition
H. Yoshida,* K. Tanino, J. Ohshita,
A. Kunai*
5052 – 5055
Distannylation of Strained C–C Triple
Bonds Catalyzed by a Palladium Complex
www.angewandte.org
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4973
Contents
Noncovalent Interactions
F. Hof, D. M. Scofield, W. B. Schweizer,
F. Diederich*
5056 – 5059
A Weak Attractive Interaction between
Organic Fluorine and an Amide Group
A combination of a chemical doublemutant cycle and a linear free energy
relationship has demonstrated that a
weak attractive interaction ( 0.8 to
1.5 kJ mol 1) exists between an organic
fluorine substituent and the face of an
amide functional group (see picture). This
study supports recent results that have
suggested that such an attraction may be
operative in enzyme–inhibitor interactions.
Host–Guest Systems
T. Kawase,* N. Fujiwara, M. Tsutumi,
M. Oda,* Y. Maeda, T. Wakahara,
T. Akasaka*
5060 – 5062
Supramolecular Dynamics of Cyclic
[6]Paraphenyleneacetylene Complexes
with [60]- and [70]Fullerene Derivatives:
Electronic and Structural Effects on
Complexation
Stable inclusion complexes are formed
between a carbon nanoring and C70 as well
as methano[70]fullerene derivatives. 1H
NMR spectroscopic studies show that at
low temperatures the guest molecules are
situated either above or below the center
of the cavity. The presence of the bulky
ester groups results in the interconversion
between the complexes (see scheme, DG°
11.0 kcal mol 1) being faster than
decomplexation.
Four molecules are coupled together by
the single treatment of aryl boronic acids
with alkynes in the absence or presence of
iodobenzene under palladium catalysis to
afford 1,4-diaryl-1,3-butadienes as the
major product. Addition of a silver salt as
oxidant and/or base effectively enables
the selective catalytic production of the
p-conjugated compounds.
Efficient and stable chiral monodentate
phosphine ligands can be used in the
ruthenium-catalyzed enantioselective
hydrogenation of b-ketoesters (see
scheme). The catalysts are remarkably
temperature-tolerant, and enantioselectivities of up to 95 % ee are possible, even
at 100–120 8C. R = C6H5, p-CH3OC6H4,
p-CF3OC6H4, iPr, Et, C6D5.
Multicomponent Coupling
T. Satoh, S. Ogino, M. Miura,*
M. Nomura
5063 – 5065
Synthesis of Highly Substituted
1,3-Butadienes by Palladium-Catalyzed
Arylation of Internal Alkynes
Enantioselective Hydrogenation
K. Junge, B. Hagemann, S. Enthaler,
G. Oehme, M. Michalik, A. Monsees,
T. Riermeier, U. Dingerdissen,
M. Beller*
5066 – 5069
Enantioselective Hydrogenation of
b-Ketoesters with Monodentate Ligands
4974
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2004, 43, 4968 – 4976
Angewandte
Chemie
Reaction Kinetics
The variation of the activation enthalpy for
surface oxygen exchange
1
=2 O2 + VOCCQOxO + 2 hC with sample
composition in (Ln,Sr)(Mn,Fe,Co)O3 z
perovskites is rigidly coupled to the
variation of the overall reaction enthalpy
(see picture). This is the first mechanistically well-established example of a
Hammett-like relationship for inorganic
gas-solid reactions.
R. Merkle, J. Maier,*
H. J. M. Bouwmeester
5069 – 5073
A Linear Free Energy Relationship for GasSolid Interactions: Correlation between
Surface Rate Constant and Diffusion
Coefficient of Oxygen Tracer Exchange for
Electron-Rich Perovskites
Molecular Devices
L. Fabbrizzi,* F. Foti, S. Patroni,
P. Pallavicini,* A. Taglietti* 5073 – 5077
pH-driven double Cu2+ ion translocation
occurs inside an heteroditopic macrocycle. The movement opens and closes
the system allowing or preventing it to
function as receptor for bidentate anions.
When imidazole is added to a solution
buffered at an appropriate pH value,
opening of the system and substrate
binding can be induced by the substrate
itself, which results in a sharp color
change (see picture).
Porphyrinoids
A covalently linked N-fused porphyrin
dimer was synthesized by treatment of the
monomer with Ag(OCOCF3). Subsequent
reaction of this dimer with NaOMe led to
a porphyrin dimer with two a,b-bound
(“confused”) pyrrole rings (see scheme)
which adopt the inverted conformation.
The dimer exhibits aromaticity in spite of
its highly distorted structure.
T. Ishizuka, A. Osuka,
H. Furuta*
5077 – 5081
Inverted N-Confused Porphyrin Dimer
The use of ancillary ligands resulted in the
formation of (trans-[PtCl3(OH2){NK =C(OCH3)CH2CH2CL H2}2]+ (see structure), the first intermediate aqua species
in the oxidation of platinum(ii) to platinum(iv) to be isolated and characterized.
In chloroform this complex, but not the
corresponding chloro species, reacts with
excess Cl with O-demethylation of the
ligands, indicating the importance of the
coordinated water molecule.
Angew. Chem. Int. Ed. 2004, 43, 4968 – 4976
A Sleeping Host Awoken by Its Guest:
Recognition and Sensing of ImidazoleContaining Molecules Based on Double
Cu2+ Translocation inside a Polyaza
Macrocycle
Aqua Complexes
G. Tamasi, R. Cini, F. P. Intini, M. F. Sivo,
G. Natile*
5081 – 5084
Unusual Reactivity at a Platinum Center
Determined by the Ligands and the
Solvent Environment
www.angewandte.org
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4975
Contents
Self-Assembly
J. Du, Y. Chen*
Secret chambers: Organic–inorganic
hybrid nanoparticles (see picture) with a
complex hollow structure were prepared
by the self-assembly of a reactive block
copolymer, poly(ethylene oxide)-blockpoly[3-(trimethoxysilyl)propyl methacrylate], in DMF/water. Within these hybrid
large-compound vesicles, several cavities
are separated by crosslinked hybrid bilayers of uniform thickness.
5084 – 5087
Organic–Inorganic Hybrid Nanoparticles
with a Complex Hollow Structure
Natural Products Synthesis
A cornerstone of the RNA-binding antibiotic thiostrepton, namely the dehydropiperidine–thiazoline macrocyclic domain
(see formula), was constructed through a
hetero-Diels–Alder-type dimerization of
an azadiene and selective elaboration of
the resulting dehydropiperidine system.
K. C. Nicolaou,* B. S. Safina, M. Zak,
A. A. Estrada, S. H. Lee
5087 – 5092
Total Synthesis of Thiostrepton, Part 1:
Construction of the Dehydropiperidine/
Thiazoline-Containing Macrocycle
Natural Products Synthesis
K. C. Nicolaou,* M. Zak, B. S. Safina,
S. H. Lee, A. A. Estrada
5092 – 5097
Total Synthesis of Thiostrepton, Part 2:
Construction of the Quinaldic Acid
Macrocycle and Final Stages of the
Synthesis
The flagship of the thiopeptide class of
antibiotics, thiostrepton (see formula),
was synthesized by fusion of the quinaldic
acid moiety onto the dehydropiperidine–
thiazoline macrocycle (see above) followed by demasking of its sensitive
functionalities.
Communications labeled with this symbol have been judged by two referees as being “very important papers”.
Service
4976
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Keywords
5098
Authors
5099
Preview
5101
Angew. Chem. Int. Ed. 2004, 43, 4968 – 4976
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