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Graphical Abstract (Angew. Chem. Int. Ed. Engl. 221995)

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International Edition in English
1995
34/22
Pages
2427 - 2570
COVER PICTURE
The cover picture shows the structure of Te,(VOCI), viewed along the one-dimensional strings of re:+ and V0Cl:- ions (Te = green. CI = yellow. V = red,
0 = blue). From this perspective the impression of a stack of cubes for the Te partial
structure is particularly pronounced. The structure of the new polycation can be
derived froin the x-polonium structure or can be seen as dimers of Te:+. The rigid
framework o f the f [VOCI:-] ions certainly favors this unusual arrangement of
partially oxidized Te atoms. Further details on the structure and one-pot synthesis
from Tc and VOCI, are reported by J. Beck and G. Bock on p. 2559ff. (SCHAKAL
graphics generated on an IBM Work Station, X-ray data collection with a STOEIPS diffractometer).
REVIEWS
Simulating the reactions of enzymes is a challenge in organic synthesis. Enzymes. for
example aniine oxidases, flavoenzymes, and cytochrome P-450, are a tip from nature
that oxidation reactions can be conducted with catalysts. Complexes of low-valent
ruthenium are particularly suitable for synthetically useful conversions of amines,
alcohols, and even hydrocarbons.
Novel molecular structures and high catalytic activities make organolanthanide coinplexes hscinating objects of research. Whereas cyclopentadienyl derivatives have so
far been the main focus of interest, today highly reactive lanthanide complexes are
increasingly synthesized with other ligands. Low-coordinate dialkyllanthanide(rr)
compounds such as [Yb(C(SiMe,),] 2] had until very recently been considered impossible to isolate. The present review provides an overview of the recent developments i n this rapidly expanding area of organometallic chemistry.
Contents
S.-I. Murahashi * . _ _ _ _ _ _ . _ .2443
.___
-2465
_.___
Synthetic Aspects of Metal-Catalyzed Oxidations of Amines and Related Reactions
F. T. Edelmann* .......___..........
2466 2488
~
Cyclopentadienyl-Free O r g a n o h t h a n i d e
Chemistry
HIGHLIGHTS
Contents
Carbonyl complexes of calcium, silicon, and uranium have been prepared and exactly
characterized within the last two years-sensational discoveries if one considers that
previously, binary carbonyls of main group elements and actinides were only detected at very low temperatures as matrix-isolated species. These exciting developments
have again placed the spotlight on the rich and vital area of metal carbonyl chemistry.
J. E. Ellis.* W. Beck* ............. 2489-2491
Major protection systems developed by organisms to counter damaging environmental influences include both D N A repair processes and the immune system. The
recently determined crystal structure of a repair enzyme, which reverses the photochemical dimerization of pyrimidine bases in D N A [Eq.(a)], offers new insight into
the structural requirements of one of the most widespread D N A repair processes.
T. Carell * ...............................
New Surprises in Metal Carbonyl
Chemistry
2491 -2494
Sunlight-Damaged D N A Repaired with
Sunlight
CORRESPONDENCE
Is it prudent to compare homogeneous and heterogeneous phase reactions? One side of
this discussion on the reactivity of certain tresylates to nucleophiles such as butylamine and butdnethiol says “Yes”, but the other says “Not always”.
H. P. Jennissen * ..............................
J. F. King,* M. S. Gill ....................
2495
2495
Reactions of Neopentyl 2,2,2,-Trifluoroethanesulfonate (Tresylate) with Nucleophiles: A Model Study for the Coupling of
Nucleophiles with Tresyl Agdrose-A
Comment and the Reply
COMMUNICATIONS
Not the amine-N-Boc derivatives, but the isocyanates form in the reaction of alkyl- or
arylamines with di-tert-butyl dicarbonate ((Boc),O) in the presence of a catalytic
amount of 4-dimethylaminopyridine (DMAP) according to Equation (a). The procedure provides a simple laboratory method of generating sterically hindered alkyl
and aryl isocyanates without the use of phosgene.
R-NH,
+ (Boc),O
DMAP(cat)
H.-J. Knolker,* T. Braxmeier,
2497-2500
G . Schlechtingen ....................
A Novel Method for the Synthesis of
Isocyanates Under Mild Conditions
* R-N=C=O
25 C , 10min
The readily accessible P-H-functionalized half-sandwich phosphenium complexes l a
(R = tBu, sMes) are characterized by a high reactivity of the P - H or the W = P bond
which is the basis for isomerization and addition reactions leading to the hydrido
complexes 2 and 3. 4 = H, Me.
W. Malisch,* U.-A. Hirth, K. Griin,
++
P-H-Functionalized Phosphenium Complexes [C,R,(OC),W=P(H)R’] (R’ = tBu,
sMes) : Synthesis, Isomerization, and
Transformation into Hydrido Complexes
Containing a tBuP(H)OH Ligdnd
w=P
eP
W=P
R
‘
oc
1
2430
/H
oc?co
2
%
O
H, !
o c 4H ; L
(-’, V C H V~rlaji.sjie.sell.s~l~~if~
mhH, D-69451 Wemlwim. I995
M . Schmeusser, 0. Fey,
U. Weis ..................................
2500-2502
3
il57i)-O~33iY5!3422-2430R 10.110+ .2SiO
Angrw. Cli~wi.Inf. Ed. En,?/. 1995. 34, No. 22
G. Dyker,* J. Korning, P. G. Jones,
P. Bubenitschek ......__........_..._
2502-2504
An unexpected rearrangement occurs when the readily accessible epoxide 1 is filtered
through alumina with toluene. The sole product formed is the spiroannelated
[3.3. I Jpropcllune 2.
Oxidative Transformations of a Pyrimidalized 1,5-Diene
1
-
2
A silanetriol and organoaluminum compounds react
smoothly to give aluminosilcates of the type shown,
which are soluble in organic solvents. Their cubeshaped A14Si,01 groups represent the smallest
building blocks of zeolite A. Perhaps compounds of
this type w,ill be used in the near future in rational
solid-state \yntheses under mild conditions. R ' =
(2,6-;Pr,C,H,)(SiMe,)N, R 2 = 1.4-dioxane. T H E
alkyl group.
R1.s,,o\
,O'i
R2,AII;0\S,<q
I \
0 R?-AI
,(I'
Rl.~i,o,~~r
\;
M. L. Montero, A. Voigt. M. Teichert,
I. Uson, H. W. Roesky* ._._._...
2504-2506
.R'
\"!"
Soluble Aluminosilicates with Frameworks
of Minerals
0 Si.R,
lof3
\
R?
~
~
~
Three hydrogen atoms participate in the unusual hy(PPh3)3H3Re\ 'H '
drogen bond in complex I , which is obtained when
the rhenium compound is cocrystallized with indole
'H-H1
from benzene. The structure of I was elucidated by
H M distances
means of neutron diffraction ( H N
of 1.75 a n d 2.25 A). The energy of the hydrogen bond was determined by IR
spectroscopy ( A H ' = 4.3 f 0.5 kcalmol-'). All these values were also reproduced
by theoretical calculations. Indole may be a useful additive for crystal growing in
general.
J. Wessel, J. C. Lee, Jr., E. Peris.
G. P. A. Yap, J. €3. Fortin. J. S. Ricci,
G. Sini, A. Albinati,* T. F. Koetzle,*
A new form of selenium, neutral cyclo-Se,, (see picture). is entrapped within ionic layers of the title
compound. It arises from the hydrothermal reaction
between (NH,),MoS, and Na,S,Se,. The D,,-symmetric twelve-membered ring is embedded in a trigonal lattice of [Mo3(S1,,72Se1,28)]2~
clusters and
ammonium cations. The title compound forms
black. hexagonal platelets.
R. A. Stevens. C. C. Raymond,
P. K . Dorhout * _.__.........__......
2509-251 1
8
t..
Cyclooctapyrroles such as 1-3
tend to form during the condensation of dipyrrolic units if cyclization to cyclotetrapyrroles is
hindered for conformational reasons. These macrocycles are chiral and might afford interesting
complexes with metal ions. Their
most intriguing feature is their
unusual figure-eight conforniation.
0. Eisenstein,* A. L. Rheingold.*
R. H. Crabtree* _____.._...________..
2507-2509
An Unconventional Intermolecular ThreeCenter N-H . ' ' H,Re Hydrogen Bond in
Crystalline [ReH,(PPh,),]~indole.C,H,
Hydrothermal Synthesis of a Novel Se,,
Ring in [ j ( " A I M o , S , I 7zsel.281)2[Se,211
E. Vogel,* M. Broring, J. Fink, D. Rosen,
H. Schmickler. J. Lex, K . W. K . Chan,
Y-D. Wu,* D. A. Plattner. M. Nendel,
K . N. Houk* ..___..........
. _ _ . _ . . .2511-2514
.
From Porphyrin Isomers to Octapyrrolic
"Figure Eight" MacrocScles
1
The formal exchange of the pyrrole units of porphyrin
by bipyrrole units provides the title compound 1. The
hexadecaethyl derivative of 1 is the only isolable
product of a MacDonald condensation of tetrapyrrolic as well as of dipyrrolic components. The
new cyclooctapyrrole adopts a figure-eight conformation in the solid state as well as in solution.
2
fyJ
3
HN
/
NH
c
-N
\
- \'
N
1
\
'
/
M. Broring, J. Jendrny, L. Zander,
H. Schmickler, J. Lex. Y.-D. Wu.*
M . Nendel. J. Chen, D . A. Plattner,
K . N. Houk,* E. Vogel* ....... 2515-2517
Octaphyrin-(I .O. 1 .O. 1.0.1.O)
Contents
How is dioxygen activated by “naked” or ligated metals? Details of the potential
energy surfaces of the three representative cations [Fe,O,]+, [Cr,O,]+, and
[CH,Re(O,),O]
were correlated with mass spectrometric data. The results may
lead to a better understanding of 0, activation in synthetic, industrial, and biological processes.
D. Schroder, A. Fiedler, W. A. Herrmann,
H. Schwarz* ____......___.......__....
2517-2520
+
A tetrasaccharide, nilic acid, and jalapinolic acid served as building blocks in the total
synthesis of calonyctin A ( I ) ( n = 1, 2). The conformation of this amphiphilic
glycolipid was studied in micellar solution by N M R spectroscopy and molecular
dynamics simulation.
HO
Despite structural similarities, different photoreactivities are displayed by the two crystalline phases of 6-(2,4-dinitrobenzyl)-2.2’bipyridine. Whereas one phase (the arrangement of the molecules in the unit cell of this
phase is shown on the right) undergoes a photoinduced proton transfer process, the other
is photoinert. Deuteration causes a marked
increase in the lifetime of the colored phototautomer.
2520-2524
The Macrolidic Glycolipid Caloiiyctin A, a
Plant Growth Regulator: Synthesis, Structural Assignment, and Conformational
Analysis in Micellar Solution
Synthesis of Novel Tetrathiafulvalene-Based
[3]Pseudocatenanes by Self-Assembly ; Prevention of trans/c.i~Isomerization
c27
[ioo]
Z.-H. Jiang, A. Geyer,
R . R. Schmidt* ......................
Z.-T. Li, P. C. Stein, N. Svenstrup,
K . H. Lund, J. Becher* ...__.....2524-2528
Four catenanes having a tetrathiafulvalene unit in the
biscyclic macrocycle and cyclobis(paraquat-pphenylene) in the second macrocycle are described.
The TTF units locked inside the cyclophane cages
d o not isomerize even in the presence of trifluoroacetic acid. One of the four cateiianes is shown on
the right.
A mechanism has been found that explains the distribution of products
obtained in the isomerizations of
long-chain alkanes on ZSM-22 and
SAPO-11 catalysts so well that it
should now be possible to tailor reactions for the synthesis of branched
hydrocarbons. The reactions occur
at the external surface of the catalyst
according to a lock-and-key model
(shown on the right); thus. the classical concept of shape-selective catalysis cb,it/zin micropores is substantially
extended.
Coordination of Dioxygen in Three Representative Transition Metal Cations: FeOT,
C r O l , and [CH,Re(O,),O]+
J. A. Martens,* W. Souverijns,
W. Verrelst, R. Parton, G . E Froment,
P. A. Jacobs ...........................
2528-2530
Selective Isomerization of Hydrocarbon
Chains on External Surfaces of Zeolite
Crystals
Y. Eichen, J.-M. Lehn.* M. Scherl,
D. Haarer, J. Fischer, A. DeCian,
A. Corval,
H. P. Trommsdorff ................ 2530-2533
Photochromism Dependent on Crystal
Packing: Photoinduced and Thermal Proton-Transfer Processes in Single Crystals of
6-(2,4-Dinitrobenzyl)-2,2’-Bipyridine
aEt
The hydroxyl substituent makes it happen! Unlike the nonaromatic benziporphyrin
l a ( X = H ) . the hydroxy compound l b (X = OH) favors the fully aromatic
semiquinone tautomer 2.
,
H.
N
Me
\ \
QEt
N
/
Et
/
Et
,
Me
Et
H
N'
/
/
Et
/
Et
Et
H. Adams, N. A. Bailey, N . Debaecker,
D. E. Fenton,* W. Kanda. J.-M. Latour,*
H. Okawa, H. Sakiyama ........ 2535-2537
1
(q
co
oc
A Dinuclear (p-Carboxylato)manganese(lr)
Complex Derived from a Macrocyclic Ligand: A Structural Model for Active Sites in
Natural Systems
B. Konig,* H. Hollnagel, B. Ahrens,
P. G. Jones ............................
2538-2540
Activation of Macrocyclic Biaryl- Enediynes by Metal Ion Coordination
1
The ability of [(polyarene)Mn(CO),I+ to function as a facile manganese tricarbonyl
transfer reagent is the basis for a general synthetic route to homo- and heteronuclear
bimetallic complexes of naphthalenes and related fused ring systems such as 1, 2,
and 3.
&$
Oxybenziporphyrin, a Fully Aromatic
Semiquinone Porphyrin Analog with Pathways for 1871-Electron Delocalization
2
The cyclization temperature drops by 100 OC when the 2,2'-bipyridine moiety of
enediyne I is coordinated by a H g z + ion (as in 2). This noncovalent interaction
induces a change in conformation that is translated into a significantly increased
proclivity for Bergman cyclization. This approach could be used, in principle. to
activate strained, inactive enediyne prodrugs for cytotoxic action. tfa = F,CCO,
oc
2533-2535
N-
Even in solution only a single p-carboxylato bridge
links the metal centers in complex 1. according to
EPR studies. This feature makes the complex an
interesting structural model for the active center in
enzymes that contain two manganese atoms. In Dxylose isomerase, for example, the manganese atoms
are linked by a single bridging carboxylate(g1utamate) residue.
T
T. D . Lash* ............................
O
&
$. .
*
*
RU
co
oc
B F ~
S. Sun, C. A. Dullaghan. G. B. Carpenter.
A. L. Rieger, P. H. Rieger,
D. A. Sweigart* ..........._..__.....
2540-2542
Synthesis and Structure ol' Bimetallic q4,q6Naphthalene Complexes Containing a
Mn-Mn Moiety Bonded in a syn-Facial
Manner: A General Route to Homo- and
Heteronuclear Bimetallic Complexes of
Polyarenes
Mn(C0)3
1
2
3
Very surprising desorption behavior from silicalite is shown by n-hexane and n-heptane among the n-alkanes ranging from n-butane to n-decane. While n-hexane and
jr-heptane show a two-step desorption, longer and shorter n-alkanes desorb in a
single step. These results can be explained by commensurate freezing, a phenomenon
which was predicted very recently by computer simulations.
W. J. M. van Well, J. P. Wolthuizen.
B. Smit, J. H. C. van Hooff.
R. A. van Santen* ................. 2543-2544
Commensurate Freezing of II-Alkanes in
Silicalite
A reaction cascade consisting of a Heck coupling, cyclopropyl ring-opening, and a
domino Diels-Alder reaction proceeds in one pot. The palladium-catalyzed coupling of bicyclopropylidene (1) with vinyl iodide, even in the presence of dienophile
3. affords dendralene 2. which then reacts smoothly with 3 ( R ' = H. C0,Me;
R2 = C0,Me) to give bisadducts 4 in satisfactory yields. The key factor in this
reaction sequence is that the carbopalladation of the unusual tetrasubstituted alkene
I proceeds more rapidly than the Heck reaction with the dienophile.
S. Brlse, A. de Meijere* ........ 2545-2547
Unprecedented Intra- and Intermolecular
Palladium-Catalyzed Coupling Reactions
with Methylenecyclopropane Type Tetrasubstituted Alkenes
R'
J. L. Stark, V. G. Young, Jr ,
E. A. Maatta*
. ..
An elusive goal-that of enforcing the interaction of
an electron donor at a polyoxometaldte acceptor in
solution -has been realized. Covalent tethering of a
ferrocenyl group to the hexamolybdate cluster was
achieved by the introduction of a ferrocenylimido
(FcN) Iigand, yielding the anion [(FcN)Mo,O,,]'~
1 (shown schematically on the right) The simple
synthesis of 1 should also be applicable to other
systems and thus may provide new opportunities in
the field of charge transfer salts with polyoxometalate anions
2547-2548
A Functionalized Polyoxometalate Bearing
a Ferrocenyhmido Ligand : Preparation
and Structure of [(FcN)Mo,0,,12-
J
L3
A nonexplosive, easy-to-handle Te-N reagent is the Li, derivative of the tris(ter.tbuty1imido)tellurite dianion 1, which can be prepared from [(tBuN)Te],(p-NtBu),
and tBuNHLi. The Te,N,Li, cage in 1 adopts a distorted hexagonal prismatic
structure. The reaction of 1 with PhPCI, or PhBClz produces the spirocycle 2 and
the four-membered ring 3, respectively.
T. Chivers,* X. Gao,
M. Parvez
2549-2551
A Te,N,Li, Cage Containing the Tris(trrfbuty1imido)tellurite Dianion
tBu
3
2
1
A. M. Castaiio, A. Aranyos. K. J. Szabo,
Strongly stabilized carbon nucleophiles such as dialkyl malonates can also attack the central carbon of
(rr-a1lyl)palladium complexes. The regiocheinistry of
the reaction (attack at the terminal o r C2 carbon
atom; see picture) is controlled by the choice of the
ligands L in the palladium complex. E = C 0 2 E t .
L = PPh,, PtBu, , P(OPh), , etc.
RrRkJ.-E.
: Blckvall* ._........_._.____.._..
2551 -2553
A
d
".
L'
'L
The compound 2 forms 35% of the photodynamic equilibrium mixture with its precursor 1. Compound 2 is the smallest known [n](l,4)naphthalenophane and the most
stable derivative of [5]paracyclophane known to date. Compound 1 was obtained in
five steps from the Dewar benzene 3.
Nucleophilic Attack on (R-Allyl)palladium
Complexes: Direction of the Attack to the
Central or Terminal Carbon Atom by
Ligand Control
D. S. van Es, F. J. J. de Kanter,
W. H. de Wolf,
F. Bickelhaupt* .....................
2553 -2555
ScooMe
6,7-Bis(methoxycarbonyl)-2,3-dimethyl-
~ c
hi,(1=2_60 nm) (cH@cooMe
(CHh
'
1
COOMe
H
~ c
COOMe
2
o o M annelated
[5](
e 1,4)naphthalenophane,
[5]Paracyclophane
the First Benzo-
COOMe
3
High-dilution conditions are not needed to bridge p e r f -butylcalix[6]arene
with 2.6-bis(bromomethyl)pyridine
giving the bimacrocycle 1 (R = H).
The concave compound 1 can incorporate 4-nitrophenol but not 2,6diinethyl-4-nitrophenol in its cavity.
and catalyzes the addition of alcohols to dipheiiylketene.
H. Ross, U. Luning* ............. 2555-2557
iBu
iBu
Concave Reagents Based on Calixarenes
iBu
i&
1
J. Lu, W. T. A. Harrison,
A. J. Jacobson * ......................
Solutions of K,[Mo(CN),J and Me,SnCI interdiffuse
to form crystals of I , a three-dimensional coordination polymer containing large channels from which
some of the solvent molecules can be removed without the collapse of the structure (section of structure
depicted on the right). The corresponding isostructural tungsten compound can be obtained
analogously starting from K,[W(CN),].
[ ( Me,Sn),Mo(('N),
2557-2559
Synthesis and Structure of the ThreeDimensional
Coordination
Polymers
[(Me,Sn),M(CN),] (M = Mo, W)
THF] 1
A distorted cube o r two four-membered rings linked
through two bonds are alternative descriptions of
the tellurium polycation Tei+ (shown on the right)
i n Te,(VOCI,)z 1 The Tei' and V0Cl;- ions in 1
both form one-dimensional chains The Te, cube
can be derived from the a-Po structure or from
paired re:+ ions
2559-2561
Te I
re:+
A Cubic Polycation in the Structure
of Te,(VOCI,),
Te4
Te3
Te4'
* 4uthor
tn whom corresoondence \liiiuld be addreszd
BOOKS
Supramolecular Chemistry. Concepts and Perspectives
Container Molecules and Their Guests
*
*
J.-M. Lehn
D. J. Cram, J. M. Cram
Kirk/Othmer Encyclopedia of Chemical Technology, Vols. 3-10
Inorganic Experiments
Sources 2439
Author Index 2567
*
. J. I. Kroschwitz
J. D. Woollins
Corrigendum 2561
J. K. M . Sanders ..............................
2563
J.-P. Dutastu ....................................
2563
F Nees .............................................
2564
J. Beck .............................................
2565
Keyword Index 2566
Preview 2568
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