Multi-Ruthenocene Assemblies on an Organostannoxane Platform. Supramolecular Signatures and Conversion to (Ru–Sn)O2

The reaction of ruthenocene carboxylic acid (RcCOOH) with [n-BuSn(O)OH]n, (Ph3Sn)2O, and (PhCH2)3SnCl afforded hexameric compounds [RSn(O)OOCRc]6, R = n-Bu (1), Ph (2), and PhCH2 (3), respectively. These possess a prismane type Sn6O6 core which supports a hexa-ruthenocene periphery. Compounds [{n-Bu2Sn}2(μ3-O)OOCRc2]2 (4) and [n-Bu2Sn(OOCRc)2](5) were formed in the reaction of RcCOOH with n-Bu2SnO in 1:1 and 2:1 reactions, respectively. Compound [t-Bu2Sn(μ–OH)OOCRc]2 (6) is a dimer containing two ruthenocene units, and it was formed in the reaction of RcCOOH with (t-Bu2SnO)3 in a 3:1 ratio. Compounds 1–6 show an extensive supramolecular organization in the solid state as a result of several intermolecular interactions. Compound 1 could be converted quantitatively to a pure phase of the binary oxide, (RuSn)O2 at 400 °C.

[1]  Mitra S. Ganewatta,et al.  Ruthenocene-Containing Homopolymers and Block Copolymers via ATRP and RAFT Polymerization , 2013 .

[2]  K. Jurkschat,et al.  Novel stannatranes of the type N(CH2CMe2O)3SnX (X = OR, SR, OC(O)R, SP(S)Ph2, halogen). Synthesis, molecular structures, and electrochemical properties. , 2012, Inorganic chemistry.

[3]  N. Metzler‐Nolte,et al.  Azidomethyl-ruthenocene: facile synthesis of a useful metallocene derivative and its application in the 'click' labelling of biomolecules. , 2011, Chemical communications.

[4]  P. Parsons,et al.  Mono- and 1,1′-Disubstituted Organoruthenium Cyclopentadiene Complexes: Synthesis, Structural Characterization, and Antitumoral Evaluation , 2011 .

[5]  C. Absalon,et al.  Ferrocenyl-terminated redox stars: synthesis and electrostatic effects in mixed-valence stabilization. , 2011, Journal of the American Chemical Society.

[6]  B. Fabre.  Ferrocene-terminated monolayers covalently bound to hydrogen-terminated silicon surfaces. Toward the development of charge storage and communication devices. , 2010, Accounts of chemical research.

[7]  Lixia Ren,et al.  Synthesis and solution self-assembly of side-chain cobaltocenium-containing block copolymers. , 2010, Journal of the American Chemical Society.

[8]  V. Chandrasekhar,et al.  Coordination polymers containing ferrocene backbone. Synthesis, structure and electrochemistry. , 2010, Dalton transactions.

[9]  G. Bernardinelli,et al.  Synthesis of highly enantiomerically enriched planar chiral ruthenium complexes via Pd-catalysed asymmetric hydrogenolysis. , 2009, Chemical communications.

[10]  A. Nafady,et al.  One-electron oxidation of ruthenocene: reactions of the ruthenocenium ion in gentle electrolyte media. , 2009, Inorganic chemistry.

[11]  D. Astruc,et al.  Giant dendritic molecular electrochrome batteries with ferrocenyl and pentamethylferrocenyl termini. , 2009, Journal of the American Chemical Society.

[12]  V. Chandrasekhar,et al.  Facile, Ambient Temperature, Double Sn–C Bond Cleavage: Synthesis, Structure, and Electrochemistry of Organotin and Organotellurium Ferrocenecarboxylates , 2008 .

[13]  T. Dian,et al.  Synthesis of nanocrystalline RuO2(60%)-SnO2(40%) powders by amorphous citrate route , 2007 .

[14]  V. Chandrasekhar,et al.  1,1‘-Ferrocenedicarboxylate-Bridged Redox-Active Organotin and -tellurium-Containing 16-Membered Macrocycles: Synthesis, Structure, and Electrochemistry , 2007 .

[15]  P. Meunier,et al.  Performances of symmetrical achiral ferrocenylphosphine ligands in palladium-catalyzed cross-coupling reactions: A review of syntheses, catalytic applications and structural properties , 2007 .

[16]  P. Thilagar,et al.  Formation of a Double-Bicapped Hexatin Phosphate Cage by a De-arylation Reaction. Synthesis and Structure of [(PhSn)6(μ-OH)2(μ3-O)2(μ-OEt)4{(ArO)PO3}4] (Ar = 2,6-i-Pr2C6H3) , 2007 .

[17]  P. Thilagar,et al.  Nanodimensional organostannoxane molecular assemblies. , 2007, Accounts of chemical research.

[18]  S. Upreti,et al.  Reactions of [η5-carboxycyclopentadiene][η4-tetraphenylcyclo butadiene] cobalt with alkyl and aryl tin oxides: Synthesis, structural studies and electrochemistry of novel monomeric and dimeric [η5-carboxycyclopentadiene][η4-tetraphenylcyclobutadiene]cobalt based stannoxanes , 2006 .

[19]  Ian W. Wyman,et al.  Synthesis and Characterization of a Ruthenocene Carboxylate Containing Ruthenium(II) Complex , 2005 .

[20]  Chun-lin Ma,et al.  Structural chemistry of mononuclear, tetranuclear and hexanuclear organotin(IV) carboxylates from the reaction of di-n-butyltin oxide or diphenyltin oxide with rhodanine-N-acetic acid , 2005 .

[21]  P. Singh,et al.  Organostannoxane-supported multiferrocenyl assemblies: synthesis, novel supramolecular structures, and electrochemistry. , 2005, Chemistry.

[22]  D. Guay,et al.  Physicochemical Characterization of Mixed RuO 2 -SnO 2 Solid Solutions , 2005 .

[23]  Herbert Höpfl,et al.  Self-assembly of diorganotin(IV) oxides (R = Me, nBu, Ph) and 2,5-pyridinedicarboxylic acid to polymeric and trinuclear macrocyclic hybrids with porous solid-state structures: influence of substituents and solvent on the supramolecular structure. , 2005, Journal of the American Chemical Society.

[24]  Preston A. Chase,et al.  Where Organometallics and Dendrimers Merge: The Incorporation of Organometallic Species into Dendritic Molecules , 2004 .

[25]  R. Boomishankar,et al.  Recent developments in the synthesis and structure of organosilanols. , 2004, Chemical reviews.

[26]  K. Schulte,et al.  Iron wheels on silicon: wetting behavior and electronic structure of adsorbed organostannoxane clusters. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[27]  H. Höpfl,et al.  A 3D hybrid network containing large spherical cavities formed through a combination of metal coordination and hydrogen bonding. , 2004, Angewandte Chemie.

[28]  A. Steiner,et al.  First example of a Sn-C bond cleaved product in the reaction of Ph3SnOSnPh3 with carboxylic acids. 3D-supramolecular network formation in the X-ray crystal structure of [Ph2Sn(OH)OC(O)(Rf)]2, Rf = 2,4,6-(CF3)3C6H2. , 2003, Chemical communications.

[29]  G. S. Andavan,et al.  Cyclophosphazene hydrazides as scaffolds for multi-ferrocenyl assemblies: synthesis, structure, and electrochemistry , 2003 .

[30]  J. Swarts,et al.  Structure and electrochemistry of various diruthenium(II, III) tetrametallocenecarboxylates , 2002 .

[31]  A. W. Cordes,et al.  Rangoli with Tin Drums: C−H- - -O Bond-Assisted Supramolecular Grids Involving Organostannoxane Clusters† , 2002 .

[32]  D. Astruc,et al.  Supramolecular gold nanoparticles for the redox recognition of oxoanions: syntheses, titrations, stereoelectronic effects, and selectivity. , 2002, Journal of the American Chemical Society.

[33]  H. Lang,et al.  Siloxane and Carbosiloxane Based Dendrimers: Synthesis, Reaction Chemistry, and Potential Applications , 2001 .

[34]  Ruíz,et al.  Molecular batteries: ferrocenylsilylation of dendrons, dendritic cores, and dendrimers: new convergent and divergent routes to ferrocenyl dendrimers with stable redox activity , 2000, Chemistry.

[35]  P. Jutzi,et al.  Results and perspectives in the chemistry of side-chain-functionalized cyclopentadienyl compounds , 2000 .

[36]  D. Astruc.  Electron and proton reservoir complexes: thermodynamic basis for C-H activation and applications in redox and dendrimer chemistry. , 2000, Accounts of chemical research.

[37]  A. Benedetti,et al.  Morphology, microstructure and electrocatalytic properties of RuO2 -SnO2 thin films , 1999 .

[38]  P. Beer.  Transition-Metal Receptor Systems for the Selective Recognition and Sensing of Anionic Guest Species , 1998 .

[39]  A. Kaifer,et al.  Synthesis, electrochemistry and cyclodextrin binding of novel cobaltocenium-functionalized dendrimers , 1998 .

[40]  D. Shriver,et al.  A One-Dimensional Array of Clusters: Na2Mo6Cl8(O2CC5H4FeCp)6·CH3OH , 1997 .

[41]  D. Astruc.  FROM ORGANOTRANSITION-METAL CHEMISTRY TOWARD MOLECULAR ELECTRONICS : ELECTRONIC COMMUNICATION BETWEEN LIGAND-BRIDGED METALS , 1997 .

[42]  D. Astruc,et al.  The Dendritic Effect in Molecular Recognition: Ferrocene Dendrimers and Their Use as Supramolecular Redox Sensors for the Recognition of Small Inorganic Anions , 1997 .

[43]  A. Bard.  Electron transfer branches out , 1995, Nature.

[44]  R. Herbst‐Irmer,et al.  Synthesis and structures of cyclic and acyclic metallasiloxanes of groups 5-7 , 1994 .

[45]  A. Albinati,et al.  Palladium-hydrogen-phosphorus bridging in a palladium(I) dimer , 1991 .

[46]  G. Gokel,et al.  Ferrocenyldimethyl-[2.2]-cryptand: solid state structure of the external hydrate and alkali and alkaline-earth-dependent electrochemical behaviour , 1991 .

[47]  S. Roe,et al.  Phenyltin trichloroacetate complexes: preparations and structures , 1989 .

[48]  C. Iwakura,et al.  Effect of Active Layer Composition on the Service Life of ( SnO2 and RuO2 ) ‐ Coated Ti Electrodes in Sulfuric Acid Solution , 1985 .

[49]  R. O. Day,et al.  A NEW STRUCTURAL FORM OF TIN OCTAHEDRALLY COORDINATED IN A DRUM-SHAPED MOLECULE , 1985 .

[50]  R. Sievers,et al.  Niedermolekulare diorganozinn-sauerstoff-verbindungen: di-t-butyl- und di-t-amylzinnoxid , 1984 .

[51]  W. Schuh,et al.  A Diorganotin Oxide with a Planar Tin‐Chalcogen Six‐Membered Ring , 1981 .

[52]  A. Bard,et al.  Electron transfer to and from molecules containing multiple, noninteracting redox centers. Electrochemical oxidation of poly(vinylferrocene) , 1978 .

[53]  S. Gubin,et al.  Chemical and electrochemical oxidation of metallocenes, reactions of metallocenes with mercury salts , 1974 .

[54]  T. Kuwana,et al.  Chronopotentiometric Studies on the Oxidation of Ferrocene, Ruthenocene, Osmocene and Some of their Derivatives1 , 1960 .