Inorganica Chimica Acta 2000: Vol 300-302 Table of Contents

27 Pages·2000·9.3 MB·English

www.elsevier.nl/locate/ica
Volumes 300—302, 30 April 2000
Contents
ee i er ES a: ee eee eee es ee kee ARR Celery XXXili
Articles
F. Albert Cotton, Carlos A. Murillo, The mixed-valent compound [Ta(hpp),][Ta-
Xiaoping Wang (CO),] has an eight-coordinate Ta(V) cation
and a six-coordinate hexacarbonyltantalate-
Inorg. Chim. Acta 300—302 (2000) 1 (—I) anion.
A compound containing two tantalum atoms in
oxidation states separated by six units
Cynthia K. Schauer, Eric J. Voss, Michal Sabat, A new mixed-metal phosphine oxo system
Duward F. Shriver has been protonated, and shown to contain a
butterfly arrangement of the metals with a
Inorg. Chim. Acta 300-302 (2000) 7 hydrogen on the Fe-Fe backbone.
Proton reactivity of butterfly oxo and sulfido clus-
ters and structural characterization of HFe,-
Mn(CO),,.(dmpm)(p1,-O)
Benno Bildstein, Michael Malaun, Holger Kopacka, Ferrocenyldiazabutadiene carbonyl com-
Marco Fontani, Piero Zanello plexes of Cr(0), Mo(0), W(0) have been
prepared, characterized, and their properties
Inorg. Chim. Acta 300-302 (2000) 16 are compared to those of other analogous
Synthesis and electrochemistry of ferrocenyldiaza- but non-ferrocenylated diazabutadiene com-
butadiene metal carbonyl complexes (Fc-DAB)M- plexes. Electrochemical measurements show
(CO), [M = Cr,Mo,W] ferrocene based, metal carbonyl localized,
and ligand centered redox processes.
Kimberly J. Smith, Andrea L. Ondracek, The reactions of mer—trans-ReOClI,(PPh,),
Nadine E. Gruhn, Dennis L. Lichtenberger, with PMe, and PEt, provide a route to ™ians-ReocKPPn,), ana Ease CCTs +
Phillip E. Fanwick, Richard A. Walton the isomers /fac—cis-ReOCl,(PR,), and \ mer-trans-ReOC! »(PRa)2
mer—trans-ReOCl1,(PR,), (R=Me or Et) iimeanaieitias, ae on
Inorg. Chim. Acta 300-302 (2000) 23 which can be converted to ReH,(PR,), ar fll x | 2) 40
(R = Me or Et) in ca. 60% yield by reaction ee ’
A comparative study of the isomers of with LiAIH, in THF and subsequent eOENCi~PR) ReH,(PRs)2
ReOCl,(PMe,), and ReOCl,(PEt,),. The isolation hydrolysis of the reaction mixtures.
and characterization of ReHPR,), and ReO-
(OEt)CL(PR,), (R= M e or Et) and the photo-
electron spectrum of ReH.(PMe,),
Elsevier Science S.A.
Contents
G. Chiericato Jr., C.R. Arana, C. Casado, Fe, Co, and Ni complexes of terdentate
I. Cuadrado, H.D. Abrufia ligands derived from diacetylpyridine exhibit
electrocatalytic activity towards the reduc-
Inorg. Chim. Acta 300—302 (2000) 32 tion of carbon dioxide. The electro-
catalytic activity, in terms of the diminution
Electrocatalytic reduction of carbon dioxide of the overpotential and increase in current,
mediated by transition metal complexes with was dependent on both the metal center and
terdentate ligands derived from diacetylpyridine the ligand.
Fernande D. Rochon, Robert Melanson, Three mixed-ligand neutral technetium com-
Pi-Chang Kong
plexes containing monodentate phosphine
and isothiocyanato ligands were synthesized
Inorg. Chim. Acta 300-302 (2000) 43
and studied by crystallographic methods.
The crystal structures of trans-Tc(P(C,H,),)>-
Synthesis of new mixed-ligands Tc complexes con-
(NCS),, trans-Tc(P(CH;),Ph),(NCS),, and
taining monodentate phosphine and _isothio-
trans - Tc(P - (OCH,)Ph,),(NCS),0.5CH,CL,
cyanato ligands. Crystal structures of complexes
were determined. The isothiocyanato ligands
Te(P(C,H,);).(NCS),, Te(P(CH,),Ph),(NCS), and
are N-bonded to Tc. Important distortions of
Tc(P(OCH,)Ph,),(NCS),-0.5CH,Cl,
the octahedron were observed in_ the
P(CH,).Ph compound, due to the bulkiness
of the four ligands located in the same plane.
Edwin C. Constable, Catherine E. Housecroft, The complex [Ru(tpy)(1)}? * (tpy = 2,2':6',2”- a
Markus Neuburger, Alain G. Schneider, terpyridine; 1 = 4’-diphenylphosphino-2,2’:6’-,
Bernhard Springler, Margareta Zehnder 2"-terpyridine) reacts with trans-[PdCl,-
. (NCMe),] to give trans -[PdCl, {(p-1)Ru-
Inorg. Chim. Acta 300-302 (2000) 49 (tpy)}.]**, and with srans-[PtCl,(NCPh),],
: +
Programmed assembly of heteromultinuclear com- oe “sage ape ora lllligepon
4 ae ° ° x 4 o La ‘ * . =
— using 4'-diphenyiphosphino-2,2 6 ,2"-terpyrt and 1 reacts with trans-[PtCl,(NCPh),] to
yield cis-[PtCl,(1),], the structure of which
has been determined for the monohydrate
and for cis-[PtCl,(1),]-CH,Cl,1.6C;H,,; sig-
nificant differences in structure are observed
dependent upon whether the solvate
molecules are able to form hydrogen-bonded
interactions with the complex.
a - mare eng | = —— Al(IIT) and Ga(III) dithiocarbamates, RAN
Vieki An 7 nm. we ° 8 ‘wan [R,NC(=S)S],M, (R= Me, Et, Bz,), have [RNCS2}2 [AIH3.NMe3] ~~;
SEAS SCT, ARES Te. Wee been prepared by the reaction of the metal |
hydrides with the parent dithiurams and S\- *SSc—ne
Inorg. Chim. . Acta 300-302 (2000) 56 also by transmetallation with1 other meat al gxcsy,q — i ies ——NR;
sale i dithiocarbamate complexes allowing their ,_ = —
rk age cre sone trivalent aluminium solid state structures to be investigated by eee nol
g ee single crystal X-ray diffraction and com-
pared with the variety of metal dithiocar-
bamate structures available in_ the
literature.
Anne M. Wilson, F.G. West, Arnold L. Rheingold, Ti (C;Hs) (6.6 - dimethylcyclohexadieny])
Richard D. Ernst (P-Me,) has been synthesized and
. characterized. The Ti—C bonds for the dmch
Inorg. Chim. Acta 300-302 (2000) 65 ligand are much shorter than those for the
Synthesis, characterization, and organic chemistry Cp ligand, reflecting stronger metal binding
of an edge-bridged half-open titanocene for dmch. The dmch ligand is still more
reactive, engaging in coupling reactions with
ketones. With two ketone equivalents, Me3—P T i
unusual 1,4 regiochemistry results which can
be explained mechanistically.
Contents
John A. Bellefeuille, Craig A. Grapperhaus, DFT calculations correlate the access-
Agnes Derecskei-Kovacs, Joseph H. Reibenspies, ability of Ni(II/I) redox couples in N.S,
Marcetta Y. Darensbourg complexes with nickel-based LUMO
energies.
Inorg. Chim. Acta 300—302 (2000) 73
Correlation of electrochemistry, nucleophilicity
and density functional calculations of the cis-
dithiolate (bme*-daco)Ni
Vivian Wing-Wah Yam, Alex Sze-Fai Kai A series of ruthenium(II) polypyridine com-
plexes with iminodiacetic acid-containing lig-
Inorg. Chim. Acta 300-302 (2000) 82 and have been synthesized and characterized.
The photophysical properties of the com-
Luminescence cation sensing by ruthenium(II)
plexes at different pH were studied. The
complexes containing an iminodiacetic acid-
cation-binding properties of these complexes
appended ligand
for lanthanide ions have been studied by
electronic absorption spectroscopy, emission
and cyclic voltammetry. The binding con-
stants K, for europium(III) and lanthanu- yom
m(III) ions have been determined. N N = 2,2'-bipyridine
Chun-An Chen, Lin Chi-Hung, J.A. Cowan A Trp80Asn mutant of Chromatium vinosum
HiPIP shows a minimal change both in E,,
Inorg. Chim. Acta 300-302 (2000) 91 for the [Fe,S,]>*/?* cluster (+33 mV) and
in electron transfer properties. The reduced
Functional role of a conserved tryptophan residue state is stable in an aerobic environment, but
of Chromatium vinosum high potential iron protein displays a more pronounced temperature-de-
pendent degradation that is mediated by un-
folding of the protein prior to degradation of
the cluster.
Andre Morneau, Bernadette T. Donovan-Merkert, The cobaltacycle shown is reduced in THF in @l 9
William E. Geiger a one-electron irreversible process yielding + il -
two non-trivial (besides CO) products: Co
Inorg. Chim. Acta 300-302 (2000) 96 CpCo(CO), and the fluorenone anion oc +, + CpCo(CO),
An electron-transfer induced migratory insertion gre the latter is pe rome - ceaedt ye
reaction originating from a 19-electron cobalt- eo ORENOR Of Cie CO RgNee ano
acyclic anion the metallacyclic Co—C bond in the putative
19-electron complex. An equilibrium between
19- and 17-electron complexes accounts for
the observed products.
Gregory T. Baxley, Alfred A. Avey, The photochemistry of Cp,Mo0O is consistent He Cp2MoO hv
Tim M. Aukett, David R. Tyler with the intermediate formation of Cp,Mo, a
result that suggests O, may also be forming
Inorg. Chim. Acta 300-302 (2000) 102 in these reactions and that Cp,MoO may be
useful as a catalyst for photochemical water-
Photoactivation of water by Cp,Mo and photo- _ splitting. However, gas chromatographic, HO [Cp2Mo] 1/2 O2
chemical studies of Cp,MoO. Investigation of a mass spectroscopic, and chemical analyses
proposed water-splitting cycle and preparation of a showed that free O, was not a product. It is
water-soluble molybdocene dihydride concluded that if O, is produced by irradia-
tion of Cp,Mo0O, it is either at a level below
our detection limits (as low as 0.02 pmol of
O,) or it is reacting too rapidly with
Cp,Mo0O to be detected.
Contents
Thomas R. Cundari, Wentao Fu A new force field was developed using
y = 0.9714x + 3.2064
genetic algorithms (GAs) to _ optimize
R? = 0.9421
Inorg. Chim. Acta 300—302 (2000) 113 molecular mechanics (MM) parameters. The
GA-MM approach was applied to the study
Genetic algorithm optimization of a molecular
of technetium (Tc) complexes with co-
mechanics force field for technetium
ordination numbers of 5 or 6 and metal
oxidation states of +3 to +6. Soft and
hard donor ligands were studied. Good
modeling was achieved in a fraction of the 80 100 120 140 160 180 200
time of quantum methods, with considerably Calculated Bond Angle (Degree)
less computational resources.
Thomas Scheiring, Wolfgang Kaim, José A. Olabe, The missing diruthenium(II,II]) compound C
Alejandro R. Parise, Jan Fiedler in the series of pyrazine-bridged mixed-valent |C N |. CN
decacyanodimetal(II,II]) complexes was M—NC_>>N—M—CN
Inorg. Chim. Acta 300-302 (2000) 125 characterized by UV-—Vis/IR spectroelectro-
| NC”|
chemistry. In comparison to the Fe and Os
The valence-localized decacyanodiruthenium-
analogues and to the decaamminediruthen- CN CN
(III,11) analogue of the Creutz—Taube ion.
ium(II,IIT) species (ie. the Creutz—
Completing the full d°/d° triad [(NC);M(p-pz)-
Taube ion) the new d°/d° system exhibits
M(CN).}°~ , M = Fe,Ru,Os; pz = pyrazine
rather weak metal—metal coupling, as M = Fe, Ru, Os
indicated by K.=10*’ (in CH,Cl,) and
agreement with the Hush model for
inter-valence charge transfer.
A. Antifiolo, F. Carrillo-Hermosilla, J. Fernandez- The thermal treatment of the complex
Baeza, A.M. Fernandez de Toro, S. Garcia-Yuste, [Nb(n°-C;H,SiMe,).(H),] with the corres-
A. Otero, J.C. Pérez-Flores, A.M. Rodriguez ponding mercapto-, hydroxy-, amino-pyri-
midine or -pyrimidine affords thiolate-, oxy-,
Inorg. Chim. Acta 300-302 (2000) 131 amido-pyridine and -pyrimidine-containing
niobocene_ derivatives. An X-ray dif-
Synthesis and characterization of thiolate, -amido,
fraction study has been carried out for
and -oxy heterocyclic-containing niobocene com-
complex [Nb(n°-C,H,SiMe,),(n?-N,S-S(C,-
plexes: X-ray molecular studies of [Nb(n°-
H,N,))] (3).
C;H,SiMe,),(n?-N,S-S(C;H-,N,))] (3)
Anthony D. Selmeczy, William D. Jones The reactions of (C;Me,)Rh(PMe,)H, with
alkynes lead to n?-olefin complexes by way
Inorg. Chim. Acta 300—302 (2000) 138 of vinyl hydride intermediates. The mech-
anism and stereochemistry of these reactions
Insertions of electrophiles into metal hydride
are discussed.
bonds. Reactions of (C,;Me.)Rh(PMe,)H, with
activated alkynes to produce n’-alkene complexes
Anne Dolbecq, Emmanuel Cadot, Dirk Eisner, The [(HPO,),Mo,S,0,(OH),}>~ anion is
Francis Sécheresse built from the association of three {Mo,SO,}
dinuclear units, connected to each other by
Inorg. Chim. Acta 300-302 (2000) 151 phosphate groups. This anion is obtained
from the sulfurated parent [(HPQO,),-
Regioselective S/O substitutions in heteropolyoxoth- Mo,S,O,(OH),}°~ through regioselective S/
ioanions: *'P NMR study and X-ray crystal structure O substitution reactions. Only the three sul-
of the half-substituted anion [(HPO,),Mo,S,0,- fur bridging atoms in the opposite side to the
(OH),}° peripheral PO, groups are substituted by
oxygen atoms.
Contents
Edwin C. Constable, Oliver Eich, Catherine
E. Housecroft, David C. Rees A pairir of of lil igands ii n whihcihc h tthhr ee or ff our
2,2’-bipyridine (bpy) metal-binding domains
are sited about a central core have been
Inorg. Chim. Acta 300-302 (2000) 158
prepared. In the case of a ligand bearing four
bpy units attached to the para-positions of a
Metallostars containing {Ru(bpy),} motifs
central tetraphenylmethane core, the tetranu-
clear complex containing four {Ru(bpy);}
units has been prepared and shown to consist
of a mixture of diastereomers.
Bernd Wrackmeyer, Oleg L. Tok, 1-Alkynyltin and l-alkynylgermanium com- Me;S BAll,
Elena Klimkina, Yuri N. Bubnov pounds R,M-C=CR'! react with triallylbo- SHG
rane, All,B, preferably by stereoselective Ph A
Inorg. Chim. Acta 300-302 (2000) 169 1,l-allylboration. Only in the case of Me3;Sn—==-Ph—> +
oe Me,Sn-C=CPh the 1,2-allylboration pro- + AllkB Me3S ro Ph
Reactivity of mono-l-alkynyltin and -germanium duct is formed in an appreciable amount. If y
compounds towards triallylborane R! is bulky (e.g. ‘Bu, SiMe, SnMe,) alkynyl/ All2B
allyl exchange is an alternative reaction. A
smooth and quantitative 1,l-allylboration jYWe,ge—==—Ph al on GP
takes place with Bu,Sn—C=CFc, Fe =(n°- + AllsB Ph V4
C.H.)Fe(n°-C;H,), providing an easy access
to alkenes bearing the ferrocenyl and the
stannyl group in geminal positions.
Joseph P. al Dulaimi, Robin J.H. Clark, The first mixed cyanide/isocyanide complexes
Marcia Saavedra S., Md. Abdus Salam of ruthenium(II) and, by electrochemical
generation, of their ruthenium(III) counter-
Inorg. Chim. Acta 300-302 (2000) 175 parts have been synthesised. All of the ruthe-
nium(II) and ruthenium(III) species have
Spectroelectrochemical studies on some new ruthe- been shown by infrared spectroscopy (IR-
nium(II) complexes containing both cyanide and RAS) to have the trans-trans-trans-octahe-
isocyanide ligands dral geometry.
B. Miiller, H. Vahrenkamp The title complex dimethylaminobenzal- S SNH
dimine — zinc - bis(pentafluorothiophenolate) a i- CeFs ae we CoFs
Inorg. Chim. Acta 300-302 (2000) 181 was obtained from the reaction of dimethyl- ae oat
aminobenzaldehyde with ammonia-contami- / \ CeFs / \ CoFs
A zinc—aldimine complex nated —_zinc-bis(pentafluorothiophenolate). 1 2
Zinc effects the catalytic formation and stabi-
lization of the aldimine by complexation.
This is the first case where the molecular
structures of the corresponding aldehyde and
aldimine complexes could be compared.
Mauro C.M. Laranjeira, Rosemary A. Marusak, Reduction of [Ni!"(Me,L)]* by [Fe!(Me,- [Ni!(Me2L)]* + [Fe!(Me2LH)]*
A. Graham Lappin LH)]*, where the ligand, Me,LH,, is
3,14 - dimethyl - 4,7,10,13 - tetraazahexadeca-
Inorg. Chim. Acta 300-302 (2000) 186 3,13-diene-2,15-dione dioxime leads to
products [Ni'(Me,LH)]* and [Fe''(Me,-
Driving force effects in proton coupled electron
L)]* where proton transfer has accompanied __[Ni!/(Me2LH)]* + (Fe!!l(Me2L)]*
transfer
electron transfer. The rate of this process is
almost three orders of magnitude faster than
expected for electron’ transfer alone,
suggesting that the acceleration results from
a coupling of the electron and proton
transfer steps.
Contents
Christian Hollatz, Annette Schier, Hubert Gold(I) complexes with phosphorous or
Schmidbaur diorganylphosphorous acid as ligands form
oligomeric aggregates with hydrogen bonds
Inorg. Chim. Acta 300-302 (2000) 191 supporting the gold—gold bonded pairs or
strings of monomers. Phosphite complexes
Gold(I) complexes with P=O and P—OH
oligomerise solely via aurophilic bonding.
functionalised phosphorus ligands
The complexes [(dcpm)NiCl,] (1), [Ni,Cl.-
Charles E. Kriley, C. Joy Woolley, Matthew K.
Krepps, Eric M. Popa, Phillip E. Fanwick, Ian P. (u-depm).(u-H)} (3), [Nix(u-PCy>).(PCy>-
Me),] (4) and [Ni(dcpm),](NO,),-2EtOH (2),
Rothwell
dcpm = bis(dicyclohexylphosphino)methane,
have been prepared and characterized by *'P,
Inorg. Chim. Acta 300-302 (2000) 200 'H NMR (or EPR) as well as X-ray crystal-
lography. The salt NiCl,-6H,O was found to
Synthesis and characterization of a series of novel
react with dcpm to form the monomeric, four
nickel(II)/nickel(I1) complexes. Crystal structures of
coordinate, diamagnetic complex [(dcpm)-
[NiCl,(depm)], [Ni(dcpm),](NO,),-2EtOH, [Ni,Cl.-
NiCl,] (1). Complex 1 was then reduced with
(udepm).(u-H)] and — [Ni,(u-PCy,).(PCy,Me),];
Bu3SnH (or LiH with heating) in toluene at
dcpm = bis(dicyclohexylphosphino)methane room temperature to form the air sensitive
‘ :
‘A-frame’ complex [Ni,Cl,(y-depm),(y-H)]
(3). The Ni-Ni bond distance for 3 was found
to be 2.904(3) A showing the lack of any
Ni-Ni metal bonding.
4
Michiko B. Inoue, [liana C. Mufioz, A chelating amide-based naphthalenophane
Motomichi Inoue, Quintus Fernando forms binuclear Zn? * and Cd?* complexes. 1°)
The ligand molecule has a_ high steric
3
Inorg. Chim. Acta 300-302 (2000) 206 constraint, and metal complexation causes
2-O<— -7
Xbi-nruacyl ears trZunc?t ur* esa nd anCdd ?* flcuoomrepslceexnecse ofs paenc taram ideo-f gstrrouucptsu rala s da efroersmulatt ioonf coonft ratchtei on napohf thtyhle 2) \ ‘ ‘ f‘ ‘ ~'4s ss (P d -
based naphthalenophane macrocyclic ring. The unique structural Q W“w---S- 2 fof
features lead to novel fluorescence properties
OX
including intensity changes with pH and with
metal complexation.
Douglas Hagrman, Pamela Hagrman, The reactions of MoO, and CuSO,°5H,O
Jon Zubieta with a variety of nitrogen donor ligands un-
der hydrothermal conditions yield organic-
Inorg. Chim. Acta 300-302 (2000) 212 inorganic composite materials constructed
from polyoxomolybdate clusters and copper-
Polyoxomolybdate clusters and copper—organo- ligand coordination complex cations. Both
nitrogen complexes as building blocks for the the organic component and the secondary
construction of composite solids metal coordination preferences may have
profound influences on the oxide microstruc-
ture.
David M.L. Goodgame, David A. Grachvogel, A number of lanthanide complexes with the
Izhar Hussain, David J. Williams bisamide ligands N,N’-p-xylylenebisaceta-
mide, N,N’-trans-1,4-cyclohexylaminebisac-
Inorg. Chim. Acta 300-302 (2000) 225 etamide, N,N’-trans-1,4-cyclohexylaminebis-
n-butyramide have been prepared and three
Polymeric lanthanide complexes with extended representative examples have been struc-
reach bisamide ligands turally characterised by X-ray diffraction
methods. The bisamide ligands bridge the
metal centres so as to form polymeric sheet
structures containing contiguous large (44- or
78-membered) rings.
Contents
Laura Valencia, Harry Adams, Rufina Bastida, The interaction of Co(II), Ni(II) and Cd(II)
Andres de Blas, David E. Fenton, nitrates and perchlorates with the 17-mem-
Alejandro Macias, Adolfo Rodriguez, bered pyridine-derived macrocycle contain-
Teresa Rodriguez-Blas ing an N,O,-donor set has been investigated.
The oxaazamacrocyclic ligand L and the
Inorg. Chim. Acta 300—302 (2000) 234 metal complexes have been fully character-
ized by conventional spectroscopic tech-
Synthesis and characterization of cobalt, nickel, niques, and the X-ray crystal structures of
zinc and cadmium compounds with a pyridine- the macrocycle L and of the complexes
derived N,O, macrocycle: Crystal and molecular [CoL}(NO;),, [NiL](NO,), and [ZnL(H,O)-
structures of the macrocyclic ligand and Co(II), (CH,CN)|(CIO,), have been determined.
Ni(II) and Zn(II) complexes
Hitoshi Tamiaki, Natsushi Matsumoto, Synthetic gadolinium(III) meso-tetraarylpor-
Satomi Unno, Satoshi Shinoda, Hiroshi Tsukube phyrinates extracted zwitterionic L-amino
acid from an aqueous solution to give a 1:1
Inorg. Chim. Acta 300—302 (2000) 243 complex in benzene or dichloromethane
through synergistic binding of both the
Induced circular dichroism active complexes of amino and carboxylic groups. The resulting
synthetic gadolinium(III) porphyrinates with chiral highly coordinated complex afforded chiral-
amino acids ity-dependent, intense circular dichroism
bands of reversed S-shape type at the Soret
region (400—450 nm).
Gregory J. Grant, Myron W. Jones, Complexation studies with Ni(II), Co(II),
Kristi D. Loveday, Donald G. VanDerveer, Co(II), Cd(II), and Cu(I]) for the two mixed
William T. Pennington, Cassandra T. Eagle, oxathia crown ligands 98,0 and 18S,0, are
Larry F. Mehne reported. The copper(II) complex, [Cu-
(9S,O),)(BF,),, shows an interesting Jahn-
Inorg. Chim. Acta 300—302 (2000) 250 Teller distortion resulting in all of the coordi-
nate bonds being remarkably similar in
Transition metal complexes with macrocyclic
length. In all of these complexes, the two
oxathiaethers
oxathiaether ligands function as much
weaker field ligands than do their crown
thioether analogs.
Martin Sperrle, Giambattista Consiglio Optically active 2-oxopentanedioates and bu-
tanedioates are accessible through multiple
Inorg. Chim. Acta 300—302 (2000) 264 carbonylation reactions of 1|-olefins catalyzed
by cationic palladium(II) complexes modified
Palladium-catalyzed enantioselective multiple car- with chiral diphosphines. Chemo-, regio- and
bonylation of 1l-olefins. Synthesis of optically ac- enantioselectivity results point towards com-
tive 2-oxo-pentanedioates and butanedioates mon intermediates for the two reactions.
Jennifer A. Harnisch, Robert J. Angelici
A conceptually new strategy for the synthesis
of large-ring, poly-donor macrocycles using
Inorg. Chim. Acta 300—302 (2000) 273
multi-metal ion templates is illustrated by the
synthesis of a 36-membered macrocycle con-
Gold and platinum benzenehexathiolate complexes
taining 12 phosphorus donors constructed on
as large templates for the synthesis of 12-coordi-
a template (C,S,Au,) consisting of benzene-
nate polyphosphine macrocycles
hexathiolate coordinated to six Au* ions
Contents
Andreja Bakac, Vjera Butkovic, The complex trans-L'(H,O)CrCH(CH,); *
James H. Espenson, Matko Orhanovic undergoes three parallel first order reactions
— homolysis (k=0.003 s~'), hydrolysis
(k~2.5x10~° s~'), and 6-elimination X | _
Inorg. Chim. Acta 300-302 (2000) 280
(k~1.9x 107° s~'). Cr
/ |\
Concurrent homolysis, B-elimination, and
hydrolysis of macrocyclic alkylchromium
complexes
R = CH(CH3)2
Kenji Nomiya, Yukinori Arai, Yasushi Shimizu, The preparation and characterization of vari-
Mizuto Takahashi, Toshio Takayama, ous salts of a tri-Ti'Y-substituted Wells—
Heiko Weiner, Toshi Nagata, Dawson-substructure polyoxoanion = are |
Jason A. Widegren, Richard G. Finke described. _ Ultracentrifugation _ solution
molecular weight (MW) experiments show 104
Inorg. Chim. Acta 300-302 (2000) 285 that this polyoxoanion exists in aggregated,
Ti-O-Ti anhydride forms, thereby illustrat- 8
Synthesis and characterization of the tetrameric, ing the importance of MW data in the cor- é
tri-titanium(IV)-substituted | Wells—Dawson-sub- rect formulation of polyoxoanions that can
x
structure polyoxotungstate, [(P,W, ;Ti,Ox, ;),}°° form anhydride bonds. 0.04
the significance of ultracentrifugation molecular
~——
weight measurements in detecting aggregated, an- 6.6 7 6.T 7 — 6.8 ” 6.T 9 ’ 7.0 71 72
hydride forms of polyoxoanions Radius
Trevor R. Griffiths, James Dixon Electron irradiation turns single crystals of
thoria blue. 3 MeV electrons transferred @-Th
Inorg. Chim. Acta 300—302 (2000) 305 sufficient energy to displace lattice oxygen 0-0
Electron irradiation of single crystal atoms, but not thorium atoms. The spectrum
thorium dioxide and electron transfer of the blue colour was similar, but not identi-
reactions cal, to that generated with neutron irradia-
tion. Defects created here are of shallow
energy and intervalence bands only occurred
in the presence of aggregates of impurity i
ions.
Nattapong Srisook, Joseph Rizzolo, A single crystal of TI[Ag(CN),] shows ‘opti- ailtees
George E. Shankle, Howard H. Patterson cal memory’. That is, the luminescence spec- (a) top-to-bottom
trum is dependent on the irradiation history § 400€+06 - e) foumane
Inorg. Chim. Acta 300-302 (2000) 314 of the crystal. A light-induced electron trans- 3 (a +a a
fer mechanism is proposed. & 3.006 +06
Light-induced electron transfer in TI[Ag(CN),]: 3
Photochemical reaction of luminescent metal- Saisie
metal exciplexes in the solid state © sesecen
0.00E + 0.6
350 400 450 500 550
Wavelength, nm
F. Albert Cotton, Lee M. Daniels, Cr,(CHIP),, where CHIP is the anion of 1’,
Carlos A. Murillo, Hong-Cai Zhou 3’ - dihydrospiro[cyclohexane - 1,2’ - [2H]-imi-
dazo[4,5-b]pyridine], has been synthesized
Inorg. Chim. Acta 300—302 (2000) 319 and crystallographically characterized. It has
a Cr—Cr distance of 2.016(1) A.
The effect of divergent-bite ligands on metal
metal bond distances in some paddlewheel com-
plexes
Contents
The compound §,11,17,23-tert-butyl-25,
Stephan Knoblauch, O. Matthew Falana,
Jaewook Nam, D. Max Roundhill, Horst Hennig, 26,27,28-(2-mercaptoethoxy) calix[4]arene re-
acts with methylmercuric acetate to give
Kornelia Zeckert
5,11,17,23 - tert- butyl -25,26,27,28 - (2 - merca-
Inorg. Chim. Acta 300—302 (2000) 328 ptoethoxy mercuriomethyl) calix[4Jarene. Se-
quential loss of dimethylmercury gives the
Calix[4Jarenes with narrow rim cluster bis-(5,11,17,23-tert-butyl-25,26,27,28-
2-mercaptoethoxy substituents as potential (2-mercaptoethoxy)) tetramercury calix[4]-
precursor molecules for metallacages and arene. 5,11,17,23-Tert-butyl-25,26,27,28-(2-
sensors mercaptoethoxy) calix[4Jarene reacts with 9-
chloromethyl-anthracene to give 5,11,17,23-
tert-butyl-25,26,27,28-(9-thiomethylanthra-
cylethoxy) calix[4]arene.
Eric S. Meadows, Leonard J. Barbour, Solid state structures of complexes formed
Frank R. Fronczek, Cheri M. Evans, between sodium cation, water, and/or
Steven F. Watkins, George W. Gokel 4,13-diaza-18-crown-6 (1) are reported. The
oxygen donor atoms of either water or the
Inorg. Chim. Acta 300—302 (2000) 333 crown participate in forming a channel-like
network of sodium cations that may emulate
Channel-like structures formed from extended
the interior of a channel’s pore.
networks of 4,13-diaza-18-crown-6 complexes
Irene B. Rother, Eva Freisinger, trans-a,Pt(I)— (a=NH,, CH,NH,) modi-
Andrea Erxleben, Bernhard Lippert fied purine base pairs and triples: Hydrogen
bonding between self-complementary pairs
Inorg. Chim. Acta 300-302 (2000) 339 and triples and heterometal (Ag* ) coordina-
tion leading to a | D helix. Purine model
trans-a,Pt(II)— (a = NH,, CH,NH,) modified
nucleobases cross-linked by trans-a,Pt(II) to
purine base pairs and triples: Hydrogen
‘metal-modified’ base pairs and triples have
bonding between self-complementary pairs and
been studied with regard to self-complemen-
triples and heterometal (Ag*) coordination
tary H bonding and heterometal binding.
leading to a | D helix
Darren S.A. George, Robert W. Hilts, The phenylacetylide-bridged heterobinuclear
Robert McDonald, Martin Cowie complex[{RhIr(CO),(u-n':n?-C,Ph)(dppm),] *
reacts with CS, and SCN"Bu at — 80°C
Inorg. Chim. Acta 300—302 (2000) 353 yielding analogous m adducts. Upon warm-
ing, the CS, adduct reacts further giving two
Sulfur—carbon bond formation and bond cleavage C,S,-containing products, one of which has
in alkynyl-bridged heterobinuclear complexes of the C,S, moiety sulfur-bound to the acetylide
rhodium and iridium 6-carbon, whereas the SCN"Bu adduct yields
a sulfide-bridged, isocyanide product by S—C
bond cleavage.
Yoshiharu Miyaki, Takafumi Onishi, Synthesis of ruthenium(II) complexes
Hideo Kurosawa chelated by the n°-arene ring and a pendent
donor atom (O, N, and P) is described. Some
Inorg. Chim. Acta 300—302 (2000) 369 alcohol chelate complexes were converted to
alkoxide complexes by treatment with bases.
Synthesis and reaction of ruthenium(II) complexes
In CH,Cl, acidity of the hydroxy proton in
containing heteroatom donor (O, N, and P)
the alcohol chelate complex was revealed to
tethered to n°-arene ring
be comparable to that of N-methylbenzyl-
ammonium cation (pX, in H,QO, ca. 11).
Contents
Zheng Wang, Arthur E. Martell, R.J. Motekaitis, _ The dinuclear ferrous complexes of two
J.H. Reibenspies macrocyclic ligands have been found to cata-
lyze the hydroxylation of cyclohexane and
Inorg. Chim. Acta 300—302 (2000) 378 adamatane.
Dinuclear Fe(II) macrocyclic complexes as cata-
lysts for the oxidation of hydrocarbons by molecu-
lar oxygen
Frédéric Berny, Rachel Schurhammer, Based on Molecular Dynamics simulations, Interface
Georges Wipff the distribution of salts of ‘symmetrical’ hard
(*, Na*, Ci-) co sok GCN, Mic,
Inorg. Chim. Acta 300—302 (2000) 384 AsPh,+, BPh,~) ions and of amphiphilic
(phospholipid; ammonium) ions is described
Distribution of hydrophilic, amphiphilic and hy-
at a water/‘oil’ interface, showing contrasted
drophobic ions at a liquid/liquid interface: a
behaviours and counterion effects. Implica- Chloroform
molecular dynamics investigation
tions for assisted ion extraction and electro-
chemistry are discussed.
Robert A. Stockland Jr., Gordon K. Anderson, The hydride-bridged palladium complexes
Nigam P. Rath [Pd,R.(u-H)(u-dppm),]PF, have been pre-
pared from [Pd,Cl,(u-dppm),] and RMgxX,
Inorg. Chim. Acta 300-302 (2000) 395 followed by CBr,, NaBH, and TIPF,. The
unsymmetrical species [PdPtR,(p-H)(p-
Synthesis and structures of hydride-bridged
dppm),]PF, was generated analogously from
palladium A-frame complexes
[PdPtCl,(u-dppm),], whereas reaction of
[Pd(Mes)(dppm),]X with [Pd,R,(y-Cl)(As-
Ph,),], followed by treatment with NaBH,,
gave [Pd,(Mes)R(y-H)(u-dppm),]PF,. The
complexes were characterized by elemental
analysis, 'H and *'P NMR spectroscopy and,
in several cases, by X-ray crystallography.
Andreas Mayr, Samyoung Ahn The oxidation of alkylidene tris(pyrazo- a
: , late)borate tungsten complexes of the type j
Inorg. Chim. Acta 300-302 (2000) 406 W(CHPh)\(X)(BHPz,)(Br) (X=imido — or NN
oxo) with bromine has been investigated with H. / \ ven
Oxidatively induced insertion of an alkylidyne unit the objective of observing a coupling process B
into the tungsten tris(pyrazolyl)borate cage of the metal—carbon multiple bond. Under / *N
the applied reaction conditions, the CPh N
group was found to insert into the tris-pyra- €o
zolyborate cage.
Yibing Shen, Keith A. Walters, Khalil Abboud, A photophysical study has been carried out
Kirk S. Schanze on the new pyridinium-substituted complex
(bpy),Ru(bpy-py-Me*)**. Temperature-de-
Inorg. Chim. Acta 300-302 (2000) 414 pendent luminescence and transient absorp-
tion studies indicate that at temperatures
Intramolecular charge transfer in pyridinium-sub-
ranging from 80 to 300 K the photophysics
stituted Ru-polypyridine complexes
of (bpy),Ru(bpy-py-Me*)** is dominated
by a low-lying Ru—bpy-py-Me* MLCT
state.