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Inorganic and Coordination Chemistry559595 INORGANIC AND COORDINATION CHEMISTRY559595 doi:10.2533/chimia.2008.595 CHIMIA 2008, 62,No. 7/8 Minisymposium Inorganic and Coordination Chemistry 149 Minisymposium Inorganic and Coordination Chemistry 150 Playing with anions: 1) Fast, environmentally friendlyruthenium- Reticular Chemistry allylation catalystsand 2) Understandingand predicting ion pairing. Omar M. Yaghi Paul S. Pregosin University of California, Los Angeles (UCLA) 607 Charles E. Young Dr. East Los Angeles,CA90095-1569 USA ETH Zurich, 8093Zurich, Switzerland This chemistryisconcernedwithlinkingorganicand inorganic molecular The lecture will consist of two separate but related themes. The opening building units into extended structures usingstrong bonds. These structures section will involve ashort excursioninto how one can synthesize new, and arecrystalline andhaveframeworks in which the inorganic units act as optimize old, rutheniumbased homogeneous allylation catalystssuch that ‘joints’ and the organicunits as ‘struts’ to produce highly porous and robust they are rapid, environmentally friendly and demonstrate exceptional metal-organic frameworks (MOFs) andzeolitic imidazolate frameworks regioselectivity,and then finish with an NMR approach designed to show (ZIFs). This presentationwill outline asimpledesign strategyand synthesis howtorecognize, understand and even predict the extent of ion pairing in a of these materials including their adsorptiveproperties and applicationsto wide variety of inorganic, organic and organometallic salts. clean energy. Inorganic and Coordination Chemistry 151 Inorganic and Coordination Chemistry 152 Multitopic Ligand Approach for theSynthesis of New Mixed Metal StericallyVery Demanding Cyclopentadienyl Ligands: Significant Compounds Changes in the Behavior of Ru Half-Sandwich Complexes FabienneGschwind, Katharina M. Fromm* Barnali Dutta,Kay Severin University of Fribourg,CheminduMusée 9, CH-1700 Fribourg, Institut desSciences et Ingénierie Chimiques, EcolePolytechnique Fédérale Switzerland de Lausanne (EPFL), CH-1015 Lausanne, Switzerland Today, the demand for new materials (superconductors,opto-electronic de- Rutheniumhalf-sandwich complexes with new cyclopentadienyl ligands vices, etc.) is steadily growing. Complexes of alkaline and earth alkaline (Cp^) have been prepared through an unprecedented Ru-catalyzed [2+2+1] metal ions mayfor example provide precursorsfor the synthesis of high-Tc cyclotrimerization reaction of tert-butylacetylene in methanol or ethanol.[1] superconductors[1, 2]. We propose the development of newheterometallic complexes with tailoredelectronic,optical and/or magnetic properties. H ♦ Onepot synthesis Combining different metal ions in molecular devices and analyzing their H Cl Cl RO ♦ Sterically demanding ligands behavior, is interesting for later applications, and also of fundamental inter- 55 °C Ru RuCl (solv.) + Ru est[3].For this purposewedevelopedamultitopic ligand system based on 3 n OR Cl ♦ Versatilestartingmaterials ROH H open polyethermolecules, which allows the coordination to different metal Cl ion types by different ligating atoms. R=Me,Et The complexes have shown distinctreactivity in stoichiometric and catalytic O O O 1. Oxalylchlorid O O O O Toluene O O O O transformations arising from the steric demand of the π-ligand. Noteworthy M O O M1I2 M1 M2I2 O 1 - - [2] 2 OH + O O O O O O O O O O O are the interplay between16e and 18e Ru-phosphine complexes. Excep- 2. Triethyamin solvent solvent N OH HO Toluene II N N N N tionalreactivity of [Cp^Ru(μ-OMe)] includes formationofCl-bridged Ru reflux,6h N N M2 2 I I dimersinstead of tetramers, unprecedented transformation of cyclooctadiene into ethylbenzene in the coordinationsphere of Ru, CO insertion in prefe- rencetoaddition and high catalytic activity forATRC reactions on awide We will showthat this concept worksbypresenting firstresults. With alka- rangeofsubstrates like N−substituteddichloro-and trichloroacetamides, lineearth metal ions such as calcium, the ligand wraps around the metal ion, [3] enamides,ethers and esters. [Cp^Ru(PTA)2]possesses increased cytotox- yielding acomplex in which the nitrogen atoms are orientedsuch as to ac- icity on human ovariancancer cell lines compared to its Cp analogue.[4] commodate another metal ion such as transition metals. [1]S.Gauthier,E.Solari, B. Dutta,R.Scopelliti,K.Severin Chem.Commun. 2007,1837 [2]B.Dutta, E. Solari, S. Gauthier, R. Scopelliti, K. Severin Organometallics 2007, 26, [1]K.M.Fromm, Dalton Transactions, 2006, 43,5103-5112. 4791 [2] R. C. Mehrotra, A. Singh,M.Bhagat, Journal of Sol-Gel Sciences [3]B.Dutta, R. Scopelliti, K. Severin Organometallics, 2008, 27,423. and Technology, 1998, 13,45-49 [4]B.Dutta, C. Scolaro,R.Scopelliti, P. J. Dyson,K.Severin Organometallics, 2008, 27, 1355. INORGANIC AND COORDINATION CHEMISTRY559696 CHIMIA 2008, 62,No. 7/8 Inorganic and Coordination Chemistry 153 Inorganic and Coordination Chemistry 154 Efficient allylation of indolesand pyrroles with allyl alcohols catalyzed Electron tunneling through rigid rod-like bridges by complexes derived from [Cp*Ru(NCMe)3](PF6): catalysis, structure and mechanism David Hanss,Mathieu Walther, Oliver S. Wenger* Alexey B. Zaitsev,Stefan Gruber, Paul S. Pregosin Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, 30 Quai Ernest-Ansermet, 1211 Geneva 4, Switzerland ETH Hönggerberg, Wolfgang-Pauli-Str.10, CH-8093 Zürich, Switzerland Photoexcitationofarhenium complexwith acovalently attached phenothia- Dicationicruthenium(IV) allyl complexes areefficient catalysts in theFrie- zine triggersanintramolecular electrontransfer that occurs via atunneling del-Crafts allylation of phenolsand indoles.1,2 We have found that mechanism.Time-resolved luminescence and transientabsorption spectros- [Cp*Ru(NCMe)3](PF6)together with selectedacidco-catalysts in thepres- copy are used to extract information on both the photoinduced (forward) and ence of allylalcohols allows for in situ formationofη3-allyl Ru(IV) com- thermal(backward) electron tunnelingrates. plexes that efficiently catalyze the reaction of indoles and pyrroles with allyl alcoholstoform3-allylindoles and 2(5)-allylpyrroles, respectively,under mild conditions in high yield and regioselectivity. Ar [Cp*Ru(NCMe)3](PF6)(5mol %) R2 Ar HA (5 mol%) R2 Ar R2 + MeCN, r.t. + N OH N N R1 R1 R1 HA -Brønstedacid Aspects of the catalysis, structure andmechanismwill be presented. 1 I. Fernandez, R. Hermatschweiler, F. Breher, P. S. Pregosin, L. F. Veiros, Moleculeswith up to five p-xylenespacers have been prepared in good M. J. Calhorda,Angew. Chem., Int. Ed. 2006, 45,6386. yields. 2 A. B. Zaitsev,S.Gruber, P. S. Pregosin, Chem.Commun. 2007,4692. Of key interest to us is the question how the electronic structure of the cova- lent bridge between the donor and theacceptor affects the electron tunneling rates. Inorganic and Coordination Chemistry 155 Inorganic and Coordination Chemistry 156 AMacrocylic Triruthenium(II)Complex Mononuclear Organometallic Pt(II) Complexes and Pt(II)-Cu(I)Mixed- Metal Complexesfrom Pyrazolate BasedCompartmental Ligands Roesel, P.; Zampese, J.; Schaffner, S.; Neuburger, M.; Housecroft, C. E.; Constable E. C. Marc-Etienne Moret and Peter Chen Department of Chemistry, University of Basel, Spitalstrasse 51, 4056 Basel, ETHZ, Wolfgang-Pauli-Strasse 10, 8093 Zürich, Switzerland Switzerland. In an effort towards the use of bimetallic cooperative effects in the field of Ruthenium(II) complexes containingpolypyridine ligands continue to at- platinum(II) mediated C-H activation[1], we synthesized mononuclear com- tractconsiderable interestbecause of their appealing photophysical proper- plexes of 3,5-bis(iminoacetyl)pyrazolate ligands[2] incorporating the tiesand their incorporationinto light-activated devicesorphoto-activated [Pt(II)Me(SMe2)], [Pt(II)Ph(SMe2)] and[Pt(II)Ph2]fragments. The coordi- molecularmachines. nation of these complexes to Cu(I)was studied, affording heteropolymetal- Herein we describe the synthesis of amononuclear ruthenium(II)complex 1, liccompounds[3]. Thesewere structurallycharacterized,and their dynamic and its cyclic trinuclear homologue 2.Bothcomplexes can be synthesized properties in solution were studied by variable temperature 1HNMR. Dative in high yields (90%) startingfromthe corresponding ligands and [cis- Pt(II)-Cu(I) bondsand cuprophilic interactions were observed in the Ru(bpy) Cl ]and are kinetically and thermodynamically stable. 2 2 [Pt(II)Ph2]containing structures. Ar Ar S Pt N CuCl2 ArN Pt NAr Pt NAr N N H N N Cu N N Cu N N N N N Ar Cu N Redox and UV-Vis and fluorescence spectroscopic properties of both com- N N NAr Pt S Ar Ar N plexes have been investigated, and the results will be presented. Ar Ar-=4-MeOC6H4-, 2,6-Me2C6H3- [1] Balzani, V.; Scandola,F.Supramolecular Photochemistry,Horwood, Chichester, 1991. [1]M. Lersch, M. Tilset, Chem. Rev., 2005, 105, 2471. [2]Balzani, V.; Campagna, S.; Denti, G.;Juris, A.; Serroni, S.; Venturi, M. [2]G. Noël, J. C. Röder, S. Dechert, H. Pritzkow,L.Bolk, S. Mecking, F. Acc. Chem.Res. 1998, 31,26. Meyer, Adv. Synth. Catal., 2006, 348, 887 [3] Badjic,J.D.; Balzani, V.; Credi, A.; Silvi, S.; Stoddart, J. F. Science [3] M.-E. Moret,P.Chen, Submitted. 2004, 303,1845, and refs. therein. INORGANIC AND COORDINATION CHEMISTRY559797 CHIMIA 2008, 62,No. 7/8 Inorganic and Coordination Chemistry 157 Inorganic and Coordination Chemistry 158 ColourimetricSensing of Cyanide with Vitamin B12 Dramatic conformational changeinthe enzymemethyl-coenzyme M reductase(MCR) when the coenzyme
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