bluuebunny/crossref_metadata_2025_split huggingface dataset:
Organocobalamin Reactions Relevant to the Mechanism of the α-Methyleneglutarate Mutase Enzyme [1]
Authors: Grate Jay W. , Schrauzer Gerhard N. 
Published: February 2015

Abstract
The organocobalamin with methylitaconic acid attached to cobalt via its methyl group has been synthesized for the first time. This compound is believed to be an intermediate in the interconversion of methylitaconic acid and α-methyleneglutaric acid, catalysed by the coenzyme B12-dependent α-methyleneglutarate mutase enzyme. Reactions of this organocobalamin and the corresponding dimethyl ester demonstrate that cleavage of the Co-C bond leads to the rearranged α-methyleneglutarate structure under conditions where intermediate carbanions are formed.
Activated Nitriles in Heterocyclic Synthesis: The Reaction of Substituted Cinnamonitriles with 2-Functionally Substituted Methyl-2-thiazolin-4-one Derivatives
Authors: Sadek Kamal Usef , Hafez Ebtisam Abdel Aziz , Mourad Abo-Elfetouh E. , Elnagdi Mohamed Hilmy 
Published: February 2015

Abstract
A variety of thiazolo[2,3-a]pyridine and 3-(2-thiazolin-2-yl)pyridine derivatives were synthesised via the reaction of arylsubstituted cinnamonitrile derivatives with 2-functionally substituted 2-thiazolin-4-one derivatives. Thiazolo[2,3-a]pyridines were also obtained on reacting arylsubstituted cinnamonitriles with thioglycolic acid in ethanolic triethylamine solutions.
Elektronenspinresonanz-Untersuchungen an Amavadin, einem vanadiumhaltigen Naturstoff / Electron Spin Resonance Investigations of Amavadine, a Natural Product Containing Vanadium
Authors: Krauß P. , Bayer E. , Kneifei H. 
Published: February 2015

Abstract
ESR spectra indicated that amavadine contains tightly bound oxovanadium (IV ). Identical ESR spectra were obtained from biological material as well as from isolated and synthesized amavadine. The ESR hyperfine structure of oxidized amavadine can be interpreted assuming the formation of a nitroxyl radical.
BaTe3, das erste binäre Erdalkalipolytellurid / BaTe3, the First Binary Alkaline Earth Polytelluride
Authors: Cordier Gerhard , Schwidetzky Christoph , Schäfer Herbert 
Published: February 2015

Abstract
BaTe3 crystallizes in the tetragonal system (space group: P421m) with the lattice constants:
a = 791.5(3) pm , c = 443.0(5) pm, c/a = 0.560.
The new compound is isotypic to BaS3 and BaSe3 and contains bent Te3 anions.
Classical One Step Syntheses of Monoand Di-Nitrate Sugars via Triflates
Authors: Afza Nighat , Malik Abdul , Voelter Wolfgang 
Published: February 2015

Abstract
A new approach for the synthesis of some sugar nitrates is described. The reaction sequence consists of esterifying partially protected carbohydrates with trifluoromethanesulfonic anhydride and reacting the resulting triflates with tetrabutylammonium nitrate. This procedure is mild, convenient and has the advantage of protecting highly acid-labile groups.
Metallacycloalkane, VIII η5-Cjclopentadienyl-η2-methylencyclopropan-Cobaltkomplexe und deren Umwandlung in η4-Butadien-Cobaltkomplexe über Cobaltacyclopentane/ Metallacycloalkanes. VIII η5 -Cyelopentadienyl-η2-Methylenecyclopropane Complexes of Cobalt and their Transformation into η4-Butadiene Complexes via Cobaltacyclopentanes
Authors: Binger Paul , Martin Tony Ronald , Benn Reinhard , Rufińska Anna , Schroth Gerhard 
Published: February 2015

Abstract
The η5-cyclopentadienyl-bis(η2-methylenecyclopropane)cobalt complexes 5 and 6 were prepared by reaction of CpCo-bis(ethylene) (4) with methylenecyclopropane (1) and 2,2,3,3-tetramethylm ethylenecyclopropane (2), which on heating isomerise via non-isolable cobaltacyclopentanes and 4-m ethylene-cobaltacyclohexanes to give the CpCo-1,3-butadiene derivatives 10, 11 and 12. The same type of isomerisation can be observed by reacting CpCo(triphenylphosphane)( acrylonitrile) with 1 leading to the CpCo-1,3-butadiene derivative (15). With diphenylm ethylenecyclopropane (3) only a CpCo-monomethylenecyclopropane complex is formed, which isomerises immediately to give CpCo(1,1-diphenyl-1,3-butadiene) (13) and in minor amounts the fluxional binuclear cobalt complex 14. All new cobalt complexes were fully characterised by means o f high resolution NM R spectroscopy.
Katalytische Synthese von Hydridmagnesiumchlorid aus Magnesium, Wasserstoff und Magnesiumchlorid/ Catalytic Synthesis of Hydridomagnesium Chloride from Magnesium, Hydrogen and Magnesium Chloride
Authors: Bogdanović Borislav , Schwickardi Manfred 
Published: February 2015

Abstract
THF solutions of hydridomagnesium chloride (HMgCl, 1a) can be prepared in nearly quantitative yields by hydrogenation of magnesium in THF solutions of magnesium chloride at 0 °C in the presence of a CrCl3-Mg anthracene catalyst. Concentration of saturated HMgCl solutions, or hydrogenation of magnesium under the above mentioned conditions in MgCl2-THF suspensions, lead to the formation of THF solutions of species having the approximate com position HMgCl · MgH2 or 2 HMgCl · MgH2.
Organoboron-Monosaccharides, XIII β-D-Mannofuranosides: Highly Stereoselective Syntheses and NMR Characterization
Authors: Dahlhoff Wilhelm Volker , Geisheimer Angelika , Schroth Gerhard , Mynott Richard 
Published: February 2015

Abstract
Stoichiometric reactions of 2,3:5,6-di-O-ethylboranediyl-α-D -mannofuranosyl bromide (1) with O -nucleophiles at room temperature give β-D-mannofuranosides with excellent stereoselectivities. The labile glycosides obtained are deboronated in quantitative yields and then converted to their tetra-O -acetates. The products are characterized by NMR spectroscopy.
Über die katalytische Umwandlung von Olefinen, VIII „Nacktes“ Nickel als Katalysator bei der Umalkylierung von Aluminiumtrialkylen mit α-Olefinen/ The Catalytic Conversion of Olefins, VIII „Naked“-Nickel as a Catalyst for the Transalkylation of Aluminium Trialkyls with α-Olefins
Authors: Fischer Karl , Jonas Klaus , Mollbach Alfred , Wilke Günther 
Published: February 2015

Abstract
Nickel(0)-olefin complexes such as tris(ethylene)nickel(0) (4), tris(bicycloheptene)nickel(0) (6 ), all-transcyclododecatriene)nickel(0) (26), tris(stilbene)nickel(0) (27) and bis(cyclooctadiene) nickel(0) (23) are highly active homogeneous catalysts for the transalkylation of aluminium trialkyls with α-olefins. After com pletion of the reaction the nickel(O) can be rem oved in the form of Ni(CO)4 by reaction with CO. Characteristic for the catalytic reaction is the formation of olefin-nickel-π-bonds and Ni -C -Al multi-centre-bonds. The mechanism o f the reaction is discussed with the help of m odels.
Diboran(4)-Moleküle mit Boratomen unterschiedlicher Koordinationszahl/ Diborane(4) Molecules with Boron Atoms with Different Coordination Number
Authors: Haubold Wolfgang , Hrebicek Johann , Sawitzki Gisela 
Published: February 2015

Abstract
Molecules with directly bonded boron atoms with different coordination numbers (10, 11, 12 and 13) can be prepared from suitable bifunctional bases like 6, 7, 8 or 9 and C12B - BC12 (1) in an appropriate solvent at high dilution. Properties and spectroscopic data - including 1J(11B-11B) - are described. The molecular structure of 10 was investigated by means of an X-ray structure analysis.
Nickel(0)-katalysierte Synthese von Iminen aus Isocyanaten und Aldehyden/ Nickel(0) Catalysed Synthesis of Imines from Isocyanates and Aldehydes
Authors: Hoberg Heinz , Sümmermann Klaus 
Published: February 2015

Abstract
The influence of different ligands upon the nickel(0)-catalysed formation of imines from isocyanates and aldehydes is reported. Carbonyl-free nickel(0) systems are found to be more active and provide a simple synthesis of imines. The catalysis proceeds via a five-membered metallacycle, which has been isolated and characterized.
Organoborierung von Alkinylstannanen, XIV Organoborierung von Bis(alkinyl)stannanen: Mechanismus und Anwendung der 119Sn–NMR-Spektroskopie/ Organoboration of Alkynylstannanes, XIV Organoboration of Bis(alkynyl)stannanes: Mechanism and Application of 119Sn NMR Spectroscopy
Authors: Kerschl Susanna , Wrackmeyer Bernd 
Published: February 2015

Abstract
Dimethylbis(phenylethynyl)stannane (1) reacts with trialkylboranes, BR3 (2), to give bis(alkenyl stannanes (5) (R = C2H5), 1-bora-4-stanna-2,5-cyclohexadienes (6 ) (R = C2H5, C3H7
i), 1- stanna-2,4-cyclopentadienes (7) (R = C2H5) and l-stanna-3-cyclopentenes (8 ) (R = CH3, C2H5). 13C and 119Sn NMR data prove the structure of the reaction products (5 to 8 ). 119Sn NMR is useful (i) for following the course of the reaction (mechanism!) and (ii) for quantitative analysis of the product distribution. Deorganoboration reactions play an important role in the formation of the various heterocyclic systems.
1,1-EMborierung von 1-Trimethylsilylalkinen/ 1.1-Diboration of 1-Trimethylsilylalkines
Authors: Klusik Hartmut , Pues Christine , Berndt Armin 
Published: February 2015

Abstract
1,2-Di-terr-butyl-l,2-dichlorodiborane(4) (1) and l,2-dichloro-1,2-bis(dimethylamino)- diborane(4) (2) add to 1-trimethylsilylalkines 3 a -3d to yield 1,1-bis(rm-butylchloroboryl)- alkenes (4) and 1, 1-bis(chlorodimethylaminoboryl)alkenes (5), respectively, while reaction of 1 with acetylene, trimethylsilylacetylene, 2-butine and 3-hexine leads to 1,2-bis(tert-butylchloroboryl) alkenes (7). Compounds 4, 5 and 7 are characterized by MS. 1H, 13C and 11B NMR spectroscopy.
Bis[(η3-allyl)nickel(μ,η5-2,3-dihydro-1,3-diborolyl)]nickeI-Tetradecker- Komplexe mit terminalen Allylliganden/ Bis[(η3-allyl)nickel(μ,η5-2,3-dihydro-1,3-diborolyl)]nickel Tetradecker Complexes with Terminal Allyl Ligands
Authors: Kuhlmann Thomas , Siebert Walter 
Published: February 2015

Abstract
Reactions between bis(allyl)nickel complexes and alkyl derivatives of 2,3-dihydro-1,3-diborole (1a, b) in refluxing toluene or mesitylene yield deeply colored solutions. By distillation and chromatography the first η3-allyl tetradecker complexes 8 were obtained in 4 -15% yield. In the violet residues higher molecular species are present, which could not be identified. The red, oily tetradeckers are characterized by NMR and mass spectra; their formation is discussed.
Topological Effect on MO Energies, IX. On Topologically Related 1,4-Dibora-2,3-diazarine and 1,4-Dibora-2,5-diazarine
Authors: Motoc loan , Polansky Oskar E. 
Published: February 2015

Abstract
Minimal STO-NG (N = 3, 4 and 6 ) basis set non-empirical HF SCF MO calculations have been performed for topologically related 1,4-dibora-2,3-diazarine (S) and 1,4-dibora-2,5-diazarine (T). The equilibrium geometries of these S and T isomers have been computed by symmetry-constraint geometry optimizations using the STO-3G basis set. The calculations lead to the prediction that: i) the T isomer is about 48 kJ/mole less stable than the S isomer, and ii) the π -MO energy patterns of the S and T isomers are in complete agreement with the TEMO theorem, while the bonding σ-MO eigenvalues exhibit four inversion points.
Beiträge zur Chemie des Bors, 148. Diamidobor(1+)-Kationen aus Bis(amino)borhalogeniden durch Halogenid-Abspaltung/ Contributions to the Chemistry of Boron, 148.Diamidobor(1+) Cations from Bis(amino)borhalogenides by Halide Abstraction
Authors: Nöth Heinrich , Rasthofer Bernhard , Weber Siegfried 
Published: February 2015

Abstract
Bis(amido)boron(1 + ) cations can be generated from bis(amino)-boron halides and an appropriate halide acceptor. The ease of formation of the diethylamido-2.2.6.6-tetramethylpiperidinoboron-( 1 + ) cation 5 from diethylamino-tetramethylpiperidino-boron halides has been studied and found to increase with decreasing strenght of the boron halogen bond. In the case of bis(2.2.6.6- tetramethyl-piperidino)boron fluoride AlCl3, BCl3, BBr3 and even BF3 give access to salts of the bis(tetramethylpiperidino)boron-(1+ ) cation. The tetrabromoborate salt 7c reacts with Ag-triflate to yield the corresponding tetratriflatoborate 7g. Similarly. bis(tetramethylpiperidino)boron chloride 8 , obtained from the tetrachloroborate 7b in boiling pyridine, readily gives bis(tetramethylpiperidino) boron(1 + )-tetrachlorometalates. Bis(tetramethylpiperidino)boron(1 + )-triflate is formed by reaction of 8 with AgOSO2CF3.
1,3,5-Tri-tert-butyl-2,4,6-triisopropyl-3,5-diaza-1-azonia-2,6-dibora- 4-borata[2.2.0]bicyclohexan, der erste Vertreter der Dewarborazine/ 1,3,5-Tri-tert-butyl-2,4,6-triisopropyl-3,5-diaza-1-azonia-2,6-dibora- 4-borata[2.2.0]bicyclohexane, the First Dewar Borazine
Authors: Paetzold Peter , Plotho Christoph von , Schmid Günter , Boese Roland 
Published: February 2015

Abstract
The iminoborane iPr-B ≡ N -tBu (1a), metastable at -78 °C, trimerizes to form (iPrBNtBu)3 (4a) at elevated temperatures. The determination of the molecular and crystal structure reveals 4a to be a Dewar-borazine-type molecule with two short peripheral BN-double-bonds (136 and 138 pm) and an extra-long bridge BN-single-bond (175 pm). The same trimer 4a is formed by addition of la to the diazadiboretidine-type dimer (iPrBNtBu)2, prepared independently. The ethyloboration and the azidoboration of la with BEt3 and Me3SiN3, respectively, and the cycloaddition of PhN3 to 1a follow expected patterns.
Azaborolinyl-Komplexe, XV. Bis(η5-1,2-azaborolinyI)ruthenium-Sandwichkomplexe – Darstellung und Strukturuntersuchung/ Azaborolinyl Complexes, XV. Bis(η5-1,2-azaborolinyl)ruthenium Sandwich Complexes – Synthesis and Structure Investigation
Authors: Schmid Günter , Boltsch Ottmar , Bläser Dieter , Boese Roland 
Published: February 2015

Abstract
The synthesis of bis(1-tert-butyl-2 -methyl-η5 - 1 ,2 -azaborolinyl)ruthenium (1) and bis(2-methyll- trimethylsilyl-η5 - 1 ,2 -azaborolinyl)ruthenium (2) succeeds when RuCL is reacted with the corresponding 1,2-azaborolinyl lithium compounds in THF at -70 °C. Each of the sandwich complex forms two isomers with a clockwise and an anti-clockwise conformation of the azaborolinyl rings. The anti-clockwise isomer of 1 (1a ) gives colourless crystals which were investigated by singlecrystal X-ray diffraction methods. The molecular structure shows the rings in an eclipsed orientation forming an interplanar angle of 8.6 °. The isomers of 1 as well as of 2 give different 1H and 11B NMR signals.
N-Methylcarbamoylphosphate, II. Thermische Zersetzung/ N-Methylcarbamoyl Phosphates, II. Thermal Decomposition
Authors: Seel Fritz , Klein Norbert 
Published: February 2015

Abstract
The thermal decomposition of various salts of mono-N-methylcarbamoyl and bis-N-methylcarbamoyl phosphoric acid in aprotic and protic solvents (acetonitrile, trichlorom ethane, alcohols) and in the solid state has been studied in detail. Final products are mono-, di-, poly-, and cyclophosphates, in addition phosphoric acid esters if alcohols are used as solvents; and either sym. dimethylurea or methyl isocyanate and methylamine.
The spontaneous decomposition of sparingly soluble N-methyl carbamoyl phosphates in aqueous suspensions to yield slightly soluble diphosphates demonstrates clearly that the reaction of calcium hydrogen phosphate with alkali cyanates via calcium carbam oylphosphate to give calcium diphosphate - which has been considered a prebiotic key reaction - is not a result of a special feature of the structure of the intermediate product.
Die Kristallstruktur von Di-μ-oxo-cis-dioxo-dichloro-bis(2,2′ -bipyridyl)- molybdän(V) (Mo–Mo)-Nitromethansolvat, Mo2O4Cl2(bipy)2 · CH3NO2/ Crystal Structure of Di-μ-oxo-cis-dioxo-dichloro-bis(2,2′-bipyridyl)- molybdenum(V) (Mo–Mo) Nitromethane Solvate, Mo2O4Cl2(bipy)2 ´ CH3NO2
Authors: Beck Johannes , Hiller Wolfgang , Schweda Eberhard , Strähle Joachim 
Published: February 2015

Abstract
Mo2O4Cl2(bipy)2 has been obtained by oxidation of MoCl4(bipy) with O2 in ethanol/H2O . The complex crystallizes from CH3NO2 with one solvent molecule per formula unit in the monoclinic space group P 21/n: a = 954.1(2), b = 1925.3(2), c = 1423.2(2) pm, β = 102.48(2)°, Z = 4. The characteristic unit Mo2O4
2+ of the dinuclear complex consists of two terminal oxo ligands in a cisarrangem ent and two bridging oxygen atoms forming a non-planar Mo2O2 ring. A strong Mo -Mo single bond is indicated by a short distance of 256.5 pm. The coordination of both Mo atoms is completed by a Cl atom and a chelating bipyridyl ligand.
Übergangsmetall-substituierte Phosphane, Arsane und Stibane, XLY. Einige Komplexe mit Dreiringstruktur: Aufbau aus Metallo-arsinsulfiden. Öffnung des Metallacyclus mit Phosphordonoren / Transition-Metal Substituted Phosphanes, Arsanes and Stibanes, XLV. Some Complexes with a Three Membered Ring Structure: Formation from Metallo-arsinesulfides. Opening of the Metallacycle with Phosphorus Donors
Authors: Luksza Michael , Malisch Wolfgang 
Published: February 2015

Abstract
The interaction of the metallo-arsanes Cp(OC)2(L)W - AsR2(1a -c) with elemental sulfur or selenium leads to the formation of the metallo-arsinesulfides (selenides) Cp(OC)2(L)W -AsR2(S,Se) (2a-c), which are converted to the metallacyclic complexes

(3a, b) with loss of CO on refluxing in pentane. While the

of 3b is cleaved at the W -S bond by (MeO)3P to give Cp(OC)2[(MeO)3P]W -AsMe2(S), (4), with an A s-bonded η1-thioarsinyl ligand, Me3P preferentially cleaves the W -As bond in 3b, d to produce Cp(OC)2(Me3P)W -S -AsR2 (5a, b), in which the R2As-S-unit is S-coordinated. The spectroscopic data of the new complexes are reported and discussed with respect to the dynamic behaviour of the compounds.
Metallkomplexe mit biologisch wichtigen Liganden, XXXIII. Reaktionen von α-Aminosäuren und α-Aminosäurederivaten mit Gold(III)-chlorid/ Metal Complexes with Biological Important Ligands, XXXIII. Reactions of α-Amino Acids and Derivatives there of with Gold(III) Chloride
Authors: Ambach Eberhard , Singh Mano Mohan , Nagel Ulrich , Beck Wolfgang 
Published: February 2015

Abstract
The hydrochlorides of a-aminoacid esters react with Au2Cl6 in thionyl chloride to give the ammonium salts [H3NCHRCO2R′]+AuCl4
- (R = H , Me, R′ = H , Me, Et). The X-ray structure of [H3NCH(Me)CO2Me]+AuCl4
- has been determined. The reactions of a-aminoacids with Au2Cl6 in SOCl2 afford mixtures of ammonium tetrachloroaurate(III) salts with a-amino acids, a-amino acid chlorides or a-amino acid anhydrides as amine components. Cysteine esters reduce gold(III) to give the gold(I) compounds [AuSCH2CH(N H2)CO2R]n (R = Me, Et).
Notizen: Ba3Sn2As4, eine neue Zintlphase mit Kettenstruktur/ On Ba3Sn2As4, a New Zintl Phase with Chain Structure
Authors: Eisenmann Brigitte , Jordan Hanna , Schäfer Herbert 
Published: February 2015

Abstract
The new compound Ba3Sn2As4 crystallizes in the monoclinic system (space group: P21/c, No. 14) with the lattice constants
a = 806.6(5) pm , b = 1986.1(8) pm ,
c = 793.1(5) pm , β = 112.3(1)°. The compound is isotypic to Sr3Ge2As4.
Octahedral Sn2As6 units are connected by common edges to chains.
Notizen: Reaction Product of Formaldehyd and O-Benzylhydroxylamine: A Schiff Base?
Authors: Respondek Johannes 
Published: February 2015

Abstract
200 MHz 1H and 50 MHz 13C NMR spectra were recorded from the reaction product of form aldehyd 1 and O -benyzlhydroxylamine 2 for the purpose of its structure elucidation
Notizen: A Dipole Moment Study of Prostaglandins F1α and F1β
Authors: Pappalardo Giuseppe C. , Grassi Antonio , Nicolini Marino , Lumbroso Henri 
Published: February 2015

Abstract
The experimental electric dipole moments in dioxane solution, together with the calculated dipole moments for some selected conformers, are reported for the two natural prostaglandins F1α and F1β. The results obtained are compatible with a hypothesized hairpin structure for these molecules in solution.
Das Redoxsystem Eisen/Iod: Untersuchungen in Acetonitril und Tetrahydrofuran. Eine neue Synthese für Tetraiodoferrat(III) / The Redox System Iron/Iodine: Investigations in Acetonitrile and Tetrahydrofuran. A Novel Synthesis of Tetraiodoferrate(III)
Authors: Pohl Siegfried , Saak Wolfgang 
Published: February 2015

The oxidation of iron by iodine in acetonitrile and tetrahydrofuran solution leads to specific redox equilibria. In dependence of the molar ratios of Fe and I2 the following compounds are isolated: Fe(CH3CN)6Fel4, Fe(CH3CN)6(I3)2, Fe(C4H8O)6[FeI3(C4H8O)]2.
When Et4NI is added to a tetrahydrofuran solution of FeI2 and I2, Et4NFeI4 can be obtained Evidence is presented for the stability of Et4NFeI4 to autoreduction.
A resonance Raman spectrum has been obtained for Et4NFeI4. Crystal data for the different compounds are reported.
Phosphaniminatokomplexe von Molybdän / Phosphaneiminato Complexes of Molybdenum
Authors: Schmidt Inge , Kynast Ulrich , Hanich Jürgen , Dehnicke Kurt 
Published: February 2015

We report the syntheses and IR spectra of phosphanciminato complexes of molybdenum:
(MoVCl4(NPPh3)(PPh3)] (I)
PPh4[MoIVCl4(NPPh3)(PPh3)] · 2CCl4 (II)
PPh4[MoVCl5(NPCl3)] (III)
I is obtained from [MoNCl4]2 and triphenylphosphane, or from [MoCl4(NSCl)]2 and triphenylphosphane: II was prepared by reacting MoNCl4 with triphenylphosphane followed by treatment with tetraphenylphosphonium chloride; III can be generated from PPh4[MoNCl4] with PCl3/PCl5. Complex I is paramagnetic (μeff, = 1.83 B.M., d1-configuration): II is diamagnetic (d2-system).
Synthesis, Crystal Structure and Electrochemistry of μ-Acetatodi-μ-hydroxo-bis[(1,4,7-triazacyclononane)ruthenium(III)]-tris-iodide. Characterization of Some Ru(II)—Ru(III) Mixed Valence Species
Authors: Wieghardt Karl , Herrmann Willy , Koppen Martin , Jibril Ibrahim , Hüttner Gottfried 
Published: February 2015

A series of mononuclear complexes of ruthenium containing the cyclic triamine ligand 1,4,7-triazacyclononane ([9]aneN3 = L; C6H15N3) have been prepared: [RuIIL (dmso)2Cl]Cl (dmso = dimethyl sulfoxide), [RuIIILX3] (X = C1- , Br-), [RuL2](PF6)2, [RuL(C2O4)I]. Hydrolyses of RuLCl3 under a variety of reaction conditions afford dinuclear species:
[RuIII
2L2(μ-OH)2(μ-CH3CO2)]I3·H2O , [RuIII
2L2(μ-OH)2Cl2](PF6)2, and the mixed-valence species [Ru2L2(μ-Cl)3](PF6)2. The complex [Ru2L2(μ-OH)2(μ-CH3CO2)]I3-H2O has been characterized by a single-crystal X-ray diffraction study. The compound crystallizes in the monoclinic space group P21/c with a = 14.70(1) Å , b = 19.00(1) Å , c = 9.714(7) Å , β = 99.62(7)°, and V = 2674 Å3, dcalcd = 2.37 g cm-3 for Z = 4, and mol wt 952.3. The structure was solved by direct methods using 2519 unique reflections with I > 2σ(I).
Final residuals were R1 = 0.0615 and R2 = 0.075. The structure consists of μ-hydroxo- and μ-acetato- bridged dinuclear cations and iodide anions. The observed diamagnetism and a short Ru-Ru bond distance of 2.572(3) Å are indicative of a Ru-Ru single bond. The electrochemical properties of [Ru2L2(μ-OH)2(μ-CH3CO2)]3+ and [Ru2L2(μ-Cl)3]2+ have been investigated by cyclic voltammetry, and by coulometry. Two one-electron redox processes have been identified for both complexes the first of which exhibits a reversible wave, whereas the second wave at more negative potentials is irreversible. The blue mixed valence species [Ru2L2(μ-OH)2(μ-CH3CO2)]2+ has been characterized in solution.