bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthese und Struktur zweikerniger Kupfer(II)‐Komplexe eines neuen Hexaaza‐Makrocyclus mit verbrückenden Oxalat‐ und Acetat‐Ionen
Authors: Warzeska Sabine , Krämer Roland 
Published: July 2007

Synthesis and Structure of Dinuclear Copper(II) Complexes of a Novel Hexaaza Macrocycle Containing Bridging Oxalate and Acetate IonsNon‐template Schiff base [2 + 2] condensation of pyridine‐2,6‐dicarbaldehyde with 1,4‐diamino‐2‐butyne yields the hexaazamacrocyclic ligand 1, which is converted to 2 by NaBH4 reduction of the imino groups. Two dinuclear copper(II) complexes of 2 containing oxalate and acetate ions, [(2)Cu2(μ‐C2O4)](BPh4)2 (3) and [(2)Cu2(μ‐CH3CO2)(OH2)](PF6)(NO3)0.75 (4), were characterized by X‐ray crystallography. The oxalate ligand in 3 forms a (μ‐η4:η4) bridge between the copper atoms. Compound 4 contains a syn‐anti‐bridging acetate ion. The Cu‐Cu distances are 5.315 Å in 3 and 4.746 Å in 4, respectively. Oxalate can be separated from other carboxylates in aqueous solution by selective binding to the [(2)Cu2] unit and precipitation of 3.
Synthesis, Structure and Reactivity of [(acac)AuCH(PPh2AuPPh2)2CHAu(acac)], a Complex Containing the Tridentate Ligand [HC(PPh2)2]−
Authors: Fernández Eduardo J. , Concepci Gimeno M. ÁN , Jones Peter G. , Laguna Antonio , Laguna Mariano , Lápez‐de‐Luzuriaga José M. , Rodríuez Miguel A. 
Published: July 2007

AbstractThe complex [(acac)AuCH(PPh2AuPPh2)2CHAu(acac)] (1) is obtained by various procedures: a) by reaction of [Ph3PAuCH (PPh2AuPPh2)2CHAuPPh3](ClO4) 2 with NBu4[Au(acac)Cl], b) by reaction of [ClAuCH(PPh2AuPPh2)2CHAuCl] with [Au(acac)PPh3] or with Tl(acac) and c) by reaction of [ClAuPPh2CH2PPh2AuCl] with Tl(acac). The acetylacetonato ligand can act as deprotonating agent; thus, complex 1 reacts with (phosphane)gold complexes, [Au(C6F5)2{(PPh2)2‐CH2)]ClO4, [Au(C6F5)3(PPh2CH2PPh2)] or [Au(PPh3)2]ClO4, to give the hexanuclear complexes [(C6F5)2Au{(PPh2)2CH} AuCH(PPh2AuPPh2)2CHAu{CH(PPh2)2) Au(C6F5)2](ClO4)2, [(C6F5)3Au(PPh2CHPPh2)AuCH (PPh2AuPPh2)2CHAu‐(PPh2CHPPh2)Au(C6F5)3] or [(Ph3PAu)2C(PPh2AuPPh2)2C‐(AuPPh3)2](ClO4)2, respectively. The crystal structure of 1 has been established by X‐ray crystallography and displays two independent eight‐membered rings with inversion symmetry and short transannular gold‐gold contacts. The first ab initio results for a transannular AuI‐AuI interaction are reported.
Stereospecific Ligand Substitutions in Manganese(I) Complexes
Authors: Tsai Shiou‐Chuan , Wang Hsin‐Ell , Huang Chi‐Tsuan , Yiin Lih‐Ming , Liu Shiuh‐Tzung 
Published: July 2007

AbstractTreatment of fac‐[(P2SPh‐P,P')Mn(CO)3Br] and fac‐[(PS2Ph‐P,S)Mn(CO)3Br] [P2SPh: Z = PPh2; PS2Ph: Z = SPh in CH3C‐(CH2PPh2)(CH2SPh)(CH2Z)] with silver hexafluorophosphate yields the η3‐tripodal manganese complexes [(P2SPh‐P,P',S)Mn(CO)3]PF6 (7) and [(PS2Ph‐P,S,S')Mn(CO)3]PF6 (9), respectively, whereas the reaction of CH3C(CH2PPh2)2‐(CH2SH) with Mn(CO)5Br gives directly [CH3C(Ph2‐PCH2)2(CH2S)‐P,P',S]Mn(CO)3 (11). Both ionic complexes 7 and 9 undergo stereospecifically ligand substitution upon treatment with Br−, I−, N−3, SCN− and CN− to give syn‐fac‐[(P2SPh‐P,P')Mn(CO)3X] and syn‐fac‐[(PS2Ph‐P,S)Mn(CO)3X] (X = Br, I, SCN, N3, CN) respectively, but the neutral complex 11 fails to undergo such a substitution reaction with these ions. However, reaction of I− with the complex [(PSMe)‐P,P',S]Mn(CO)3]BF4 (20) [P2SMe = CH3C(CH2‐PPh2)2(CH2SCH3)), which is obtained from the S‐alkylation of 11 with (CH3)3OBF4, affords syn‐fac‐[(P2SMe)‐P,P']Mn(CO)3I (22s) exclusively. The possible reaction mechanism of this ligand substitution is discussed.
Oxacycloalkenyliden‐Komplexe von Chrom, Molybdän und Wolfram: Synthese, Anellierung mit Alkinen und Diels‐Alder‐Reaktionen mit Dienen
Authors: Christoffers Jens , Dötz Karl Heinz 
Published: July 2007

Reactions of Complex Ligands, LXI[1]. ‐ Oxacycloalkenylidene Complexes of Chromium, Molybdenum, and Tungsten: Synthesis, Their Annulation with Alkynes and Diels‐Alder Reaction with DienesLithiiated propargylic ether 1 reacts with M(CO)6 (M = Cr, Mo, W) to give the 2‐oxacyclic carbene complexes 2–4 containing an α,β‐double bond and a cyclic acetal structure which serves as a protected benzoyl group. Reaction of the chromium complex 2 with tolan leads to an acyl hydroquinone derivative 5. The tungsten complex 3 undergoes a [4 + 2] cycloaddition with cyclopentadiene to give two diastereomeric oxatricyclic carbene complexes 6 and 7 with an endo/exo selectivity of 3:1. The stereochemistry of the Diels‐Alder reaction is controlled by the configuration of the acetal carbon center.
Darstellung und Komplexierung von 1,4‐Dimethyl‐2,3‐bis(isopropyliden)‐1,4‐diboratetralin
Authors: Hauß Jan , Pritzkow Hans , Siebert Walter 
Published: July 2007

Synthesis and Complexation of 1,4‐Dimethyl‐2,3‐bis(isopropylidene)‐1,4‐diboratetraline1,4‐Dimethyl‐2,3‐bis(isopropylidene)‐1,4‐diboratetraline (2) is obtained from o‐dilithiumbenzene and 2,5‐dimethyl‐3,4‐bis(chloromethylboryl)‐2,4‐hexadiene in 61% yield. Its complexation with cyclopentadienylbis(ethene)cobalt leads to the triple‐decker bis(η5‐cyclopentadienylcobalt)‐μ‐η6,η6‐1,4‐dimethyl‐2‐isopropenyl‐3‐isopropyl‐1,4‐dihydro‐1,4‐dibora‐naphthaline (3) in low yield. However, the reaction of 2 with (C5H5)Rh(C2H4)2 and (C5Me5)Co(C2H4)2 originates complexes of a tricyclic ligand formed from 2 via conrotatoric [2 + 2] cycloaddition of the isopropylidene groups. (η5‐Cyclo‐pentadienylrhodium)‐η6‐tricyclo‐[6.4.0.03,6]‐2,4,4,5,5,7‐hexamethyl‐2,7‐diboradodeca‐1,3,9,11‐tetraene (4), (η5‐pentamethylcyclopentadienylcobalt)‐η6‐tricyclo‐[6.4.0.03,6]‐2,4,4,5,5,7‐hexamethyl‐2,7‐diboradodeca‐1,3,9,11‐tetraene (5) and its related dinuclear complex 6 could be isolated in 29, 10, and 31%, respectively. Their constitutions are derived from spectroscopic data and proven by X‐ray structure analysis of 4.
Darstellung und Struktur von Allyl(tripod)cobalt(I) und der Vergleich zum analogen Cobalt(II)‐Komplex
Authors: Sernau Volker , Huttner Gottfried , Scherer Johannes , Zsolnai Laszlo , Seitz Thomas 
Published: July 2007

Preparation and Structure of Allyl(tripod)cobalt(I) and the Comparison with the Analogous Cobalt(I) ComplexThe synthesis of the 18‐electron diamagnetic allyl(tripod)cobalt(I) complex [{CH3C(CH2PPh2)3}Co(η3‐C3H5)] (1) is presented. Its structure is established by the usual analytical techniques as well as by X‐ray analysis, and it is proved to be significantly different from that of the cationic 17‐electron species 1+.
Contributions to the Chemistry of Boron, 227. The P‐centered Chemistry of [(Di‐tert‐butylphosphanyl)imino]‐(2,2,6,6‐tetramethylpiperidino)borane
Authors: Kölle Peter , Nöth Heinrich , Stolpmann Holger , Thomann Martina 
Published: July 2007

AbstractThe elements oxygen, sulfur, and selenium add to the P atom of the title borane 1. In contrast to the formation of tmpBNP(X)tBu2 (X = S, Se), the P oxide (X = O) dimerizes to [tmpBNP(O)tBu2]2 (5) with an eight‐membered flat boat‐shaped B2N2P2O2 ring. Borane 1 reacts readily with Mel to yield a phosphonium salt 8 and with BBr3 to give an adduct 9 with a BP bond. In contrast, bis(dichloroboryl)‐methane not only adds to 1 to generate a coordinate BP bond but also chloroborates the BN triple bond, the final product being a new five‐membered heterocycle 10. Similarly, the BH3 component of BH3·SMe2 first adds to the P atom of 1 followed by reaction of a second mol of BH3·SMe2 which hydroborates the BN triple bond. Finally, metal carbonyl fragments add only to the P atom of 1, demonstrating also that the chemistry of the molecule 1 is dominated by the basicity of its P center.
Synthese und Charakterisierung stabiler Bis(phosphonio)isophosphindolylium‐Carbonylmetallate und eines kationischen Bis(phosphonio)isophosphindolylium‐Gold‐Komplexes
Authors: Gudat Dietrich , Nieger Martin , Schrott Martin 
Published: July 2007

Synthesis and Characterisation of Stable Bis(phosphonio)isophosphindolyliumcarbonylmetallates and a Cationic Bis(phosphonio)isophosphindolylium‐Gold ComplexHerrn Professor Alfred Schmidpeter zum 65. Geburtstag gewidmet.
Reaction of 1,3‐bis(triphenylphosphonio)isophosphindolylium bromide, [L+][Br−] (1a), with Tl[Co(CO)4], Na[MoCp‐(CO)3], or Na[WCp(CO)3] (5a‐c) yields the corresponding ionic isophosphindolylium‐carbonylmetallates, 6a‐c. Whereas 1a fails to react with neutral metal carbonyls, a mixture of ionic complexes of the type [LAuX+][AuYZ−] (7a, X, Y, Z = Cl or Br) is formed by reaction with two equivalents of AuCl. Treatment of AuCl with the triflate [L+][OTf−] (1b), which is accessible from 1a via anion metathesis, furnishes [LAuCl+][OTf−] (7b). Both the carbonylmetallate 6c and the complex 7b have been characterized by X‐ray structure analyses. 7b displays enhanced reactivity as compared to 1b towards MeOH and H2O, forming the addition products 8 and 9a, b, the latter existing as two different diastereomers. Reactions of 7b with LiF, (Me2N)3PO, and (Et2N)2CNH), respectively, proceed via ligand exchange to yield equilibrium mixtures containing the cations [L+] and [LAuCl+].
Wasserlösliche Phosphane, IV. Tertiäre Alkylphosphane mit Ammoniumgruppen in den Seitenketten – Amphiphile mit basischen P‐Atomen
Authors: Bitterer Frank , Kucken Stefan , Stelzer Othmar 
Published: July 2007

Water‐Soluble Phosphanes, IV. – Tertiary Alkylphosphanes with Ammonium Groups in the Side Chains — Amphiphiles with Basic P‐AtomsBy stepwise aminoalkylation of PH3 with Me2N(CH2)2Cl in the superbasic medium DMSO/KOH the secondary phosphane [Me2N(CH2)2]2PH (2) is obtained in good yields. Metallation of 2 with n‐BuLi and subsequent reaction with Me2N(CH2)2]2Cl affords the basic tertiary phosphane [Me2N(CH2)2]2]3P (3), which on protonation with Ph3P · HBr in CH2Cl2 gives {[HNMe2 − (CH2)2]3P}3+ 3 Br− (4a) with an extremely high solubility in water. By oxidation of 3 with H2O2 and N‐quaternisation with Me3O+ BF the cationic phosphane oxide {[Me3N(CH2)2]3PO}3+ 3 BF (5a) is formed, which could, however, not be reduced with SiHCl3 or Si2Cl6/NEt3 to the corresponding tricationic phosphane. Tertiary cationic phosphanes of type [RMe2N(CH2)2P(Oct)2]+ X− (8a, 8b, R = Me, C8H17; X = Br, I) are accessible by free radical addition of 1‐octene to 7b and 7d. Addition of formaldehyde to 7a gives the hydroxymethyl phosphane 10a. By methylation of [RMe2N(CH2)2PH2]+I− (7d and 7e, R = CnH2n+1, n = 8, 12) with Mel under controlled condition and subsequent deprotonation of the phosphonium salts 12b and 12c the cationic tertiary phosphanes 13a and 13b with long alkyl side chains may be obtained in good yields.
Preparation and Characterization of Biologically Active Bismuth(III) Tropolonato Complexes
Authors: Diemer Rolf , Keppler Bernhard K. , Dittes Uwe , Nuber Bernhard , Seifried Volker , Opferkuch Wolfgang 
Published: July 2007

AbstractTwo new types of bismuth(III) tropolonato complexes, nitratobis(tropolonato)bismuth(III) (1d) and phenylbis(tropolonato)bismuthin (1f), are synthesized and characterized by elemental analysis, 1H‐NMR, 13C‐NMR, IR spectroscopy, and conductivity measurements. The structures of 1d and aquabis(4,5‐benzotropolonato)bismuth(III) nitrate (6b) are confirmed by X‐ray structural analyses. Derivatives of tropolone (2a) and their bismuth(III) complexes are synthesized and characterized in the same manner. Eight of these compounds are tested against Helicobacter pylori (H.p.) bacteria, which cause chronic gastritis and peptic ulcus. Most of the bismuth compounds show high in vitro activity against H.p.
Perfluororganochalkogensäuren in hohen Oxidationsstufen
Authors: Boese Roland , Haas Alois , Herkt Silke , Pryka Michael 
Published: July 2007

Perfluoroorganochalcogenic Acids in Higher Oxidation StatesPentafluoroethylseleninic acid is oxidized by KMnO4 in slightly alkaline aqueous solution to give K[C2F5SeO3]. With HClO4 the salt is converted into the free acid. Neutralisation of C2F5SeO3H with NaOH, Ag2O, NH3 + H2O provides the corresponding salts. The ethyl ester is made from Ag[C2F5SeO3] and C2H5I. Oxidation of C6F5TeC6F5 with concd. HNO3 yields C6F5Te(OH)ONO2 which on controlled hydrolyses gives (C6F5)2Te(OH)2. Strong acids like HClO4 or H2SO4 form mixed anhydrides like (C6F5)2Te(OH)ClO4 or (C6F5)2Te(OH)OS(O)2OTe(OH)(C6F5)2. For the latter compound a cyclic or noncyclic polycondensate form cannot be ruled out. Acidic 35% H2O2 solution oxidizes (C6F5)2Te(OH)2 at 40°C (48 h) to give (C6F5)2TeO2. This anhydride dissolves only in CF3SO3H forming (C6F5)2Te(OSO2CF3)4. It is soluble in CH3CN and reacts in solution with water to yield (C6F5)2Te(OH)2(OSO2CF3)2. Oxidation of C6F5TeTeC6F5 with concd. HNO3 provides oligomeric [C6F5Te(O)OH]x which still contains some HNO3. A single‐crystal X‐ray structure determination carried out on [(C6H5)4As][C2F5SeO3] shows convincingly that the central selenium atom is coordinated by three equivalent oxygen atoms with d(Se‐O) = 1.614(3) Å, proving that Se has the oxidation state VI.
Syntheses of Cyclic and Acyclic Bis(perfluoroalkylthio)nitronium Salts
Authors: Haas Alois , Waterfeld Alfred 
Published: July 2007

Abstract(F3CS)3N (1) is oxidized quantitatively by AsF5 to the first bis(perfluoroalkylthio)nitronium salt (F3CS)2N+AsF−6 (2). Addition of halide ions (F−, Cl−, Br−, l−) to the cation of 2 destroys the SNS chain. (F2CSCl)2 undergoes with ammonia a cyclization reaction to SCF2CF2SNH (3), which can be derivatized with F3CSCl or (F2CSCl)2 to SCF2CF2SNSCF3 (3a) and (SCF2CF2SNSCF2)2 (3b), respectively. Oxidation of 3a with AsF5 yields (SCF2CF2SN+AsF−6 (4) and byproducts, which suggest formation of a {3a}+• radical cation as an intermediate in this reaction. Pure 4 is accessible by reaction of 3 with AsF5 in 54% yield. The chemical and spectroscopic properties of the new species are discussed.
About some Electrophilic Substitution Reactions with [(CF3S)3C+][AsF]
Authors: Haas Alois , Waterfeld Alfred , Klare Christiane , Möller Guido , Kondratenko Nataliya V. , Yagupolskii Lev M. 
Published: July 2007

AbstractTris(trifluoromethylthio)carbenium hexafluoroarsenate (1) reacts with N,N‐dimethylaniline and anisole to form the corresponding diphenylmethanes 2, 3 with the SCF3 group at the methine carbon atom. During the reaction of 1 with benzene, compounds such as C6H5C(SCF3)3 and C6H5SCF3 are formed along with benzophenone, a product of hydrolysis of the diphenylmethane compound.
Preparation and Molecular Structures of Tetrahydrofuran, Diethylene Diglycol Dimethyl Ether and 18‐Crown‐6 Complexes of Strontium and Barium Tetrahydridoborate
Authors: Bremer Mathias , Nöth Heinrich , Thomann Martina , Schmidt Martin 
Published: July 2007

AbstractThe strontium and barium tetrahydridoborate complexes M(BH4)2 · 2 diglyme and M(BH4)2 · 18‐crown‐6 (M = Sr, Ba) have been prepared from the solvates M(BH4)2 · 2 THF by ligand displacement. 11B‐NMR and IR data reveal strongly polar bonding of the BH4 groups to the metal centers, and X‐ray structural analyses of the diglyme and crown ether compounds show molecular units in which the BH4 group is in contact via three H atoms with the metal center. In contrast, M(BH4)2 · 2 THF compounds are chain polymers in the solid state, and each metal center is surrounded by 2 THF molecules in trans position and four BH4− groups each of which forms bridges with two metal centers. Estimations of the effective radius for the BH4 group indicate a high polarity for the M‐BH4 interaction.
Pyridyl‐Functionalised Cyclopentadienyl Ligands: Building Blocks for Oligonuclear Organometallic Assemblies
Authors: Siemeling Ulrich , Vorfeld Udo , Neumann Beate , Stammler Hans‐Georg 
Published: July 2007

AbstractLithiated 2‐methylpyridine reacts with 2,3,4,5‐tetramethylfulvene (TMF) to give 2‐[2‐(2,3,4,5‐tetramethylcyclopenta‐1,4‐dien‐1‐yl)ethyl]pyridine (2H) after aqueous work‐up. Similarly, a mixture of 2‐methyl‐6‐[2‐(2,3,4,5‐tetramethylcyclopenta‐1,4‐dien‐1‐yl)ethyl]pyridine (3H) and 2,6‐bis[2‐(2,3,4,5‐tetramethylcyclopenta‐1,4‐dien‐1‐yl)ethyl]pyridine (4H2) was obtained from monolithiated 2,6‐dimethylpyridine and TMF. All three compounds were obtained as a roughly statistical mixture of double‐bond isomers. 2‐Lithiopyridine reacts with 2,3,4,5‐tetramethylcyclopent‐2‐enone to yield 2‐(2,3,4,5‐tetramethylcyclopenta‐1,3‐dien‐1‐yl)pyridine (5H) after acidic work‐up. This compound was obtained as a non‐statistical mixture of double‐bond isomers, which is presumably due to intramolecular hydrogen‐bond interactions. The lithiated derivatives 2Li, 3Li and 5Li react with iron(II) chloride to afford the respective ferrocenes (2)2Fe (8), (3)2Fe (9) and (5)2Fe (10). The structure of 10 was determined by a single‐crystal X‐ray diffraction study. The cyclopentadienyl ligands adopt a staggered conformation; the pyridyl rings are arranged in a stacked fashion with the closest ring‐ring contact being 3.16 Å. The distance between the iron atom and the cyclopentadienyl ring centroids is 1.66 Å.
On the Chemistry of Gallium, V. Cyclic Compounds of Gallium and Indium with the 2,2‐Dimethyl‐1,3‐bis‐[(trimethylsilyl)amino]propane Ligand
Authors: Linti Gerald , Nöth Heinrich , Polborn Kurt , Robl Christian , Schmidt Martin 
Published: July 2007

AbstractReaction of 2,2‐Dimethyl‐N‐lithio‐1,3‐bis[(trimethylsilyl)amino]propane (4a) with RGaBr2 (R = Br, Mes) allows the isolation of the cyclic monomeric amine(amino)gallanes 5 and 6. The cyclic bis(amino) gallanes 7 and 9 as well as the indium homologue 10 were obtained by reaction of gallium halides RGaCl2 (R = Cl, Mes) or InCl3 with dilithiated 4. In the case of R = Mes the product is a monomer. In addition, the tetrakis(amino)gallate 8 was isolated. Single‐crystal X‐ray diffraction studies confirmed the constitutions. Compound 5 has one short GaN single bond (184 pm) and a longer GaN dative bond (204 pm). Compound 7 exhibits a central asymmetrical four‐membered Ga2N2 ring [d(GaN) = 199.4, 205.6 pm] with syn‐oriented substituents. The terminal GaN bond length is 184.3 pm. Two nitrogen atoms bridge the lithium and gallium atom in the gallate 8 [d(LiN) = 206 pm]. Two Li‐H contacts complete the coordination sphere at the lithium atom.
Metallkomplexe unsymmetrisch überbrückter [N4]‐Makrocyclen: Synthese, Struktur und Redoxverhalten
Authors: Jäger Ernst‐Gottfried , Keutel Heike , Rudolph Manfred , Krebs Bernt , Wiesemann Frank 
Published: July 2007

Metal Complexes of Unsymmetrically Bridged [N4] Macrocycles: Synthesis, Structure and Redox BehaviourMetal complexes M‐5a (M = Cu, Ni, Co, Fe, and I‐Fe11) of 6,13‐Di(ethoxycarbonyl)‐7,12‐dimethyl‐benzo[b]‐1,4,8,11‐tetraaza‐cyclotetradeca‐2,5,7,11,13‐pentaene and the free ligand H2‐5a have been synthesized. The crystals of Cu‐5a · H2O and Ni‐5a · H2O consist of planar complex molecules which are linked by H bridges between the water molecules and the peripheric ester groups to give 1D chains. The average M‐N distances are equal for both complexes (Cu 1.928, Ni 1.924 Å), being unexpectedly large for the nickel complex. The redox properties of all the new compounds as well as some acetyl derivatives M‐5b have been examined by cyclic voltammetry and compared with those of the previously reported symmetrically phenylene (M‐4) and ethylene (M‐6) bridged derivatives. All complexes give a reversible single electron reduction which clearly shows the increasing electron density around the central atom in the order M‐4 < M‐5 < M‐6. Like the carbonyl substituted tetraazaannulenes M‐4 the copper complexes Cu‐5 give two, the cobalt complexes Co‐5 three, and the iron complex Fe‐5a probably four reversible single electron oxidations. They can be attributed to the species [MIIIL−II]+, [MIILo]2+, [MIIILo]3+, and [FeIVLo]4+ with Lo being a “non innocent” neutral 1,2‐quinodiimine ligand. Very surprisingly, since in contrast to Ni‐4 and Ni‐6, the nickel complexes Ni‐5 gave no reversible oxidation.
Sulfur Compounds, Part 186. The Synthesis of Cyclic Organosulfur Compounds from (C5H5)4Ti2C2S4 by Ligand Transfer Reactions
Authors: Steudel Ralf , Westphal Ursula , Pickardt Joachim 
Published: July 2007

AbstractThe tetrathiaoxalate complex Cp4Ti2C2S4 (1) reacts with an equimolar amount of COCl2 to give the blue‐green mononuclear complex Cp2TiC2S4CO (4). This reaction is analogous to the known reactions of 1 with SCl2 or S2Cl2. However, when 1 was treated with equimolar amounts of the bifunctional sulfenyl chlorides 1,2‐C2H4(SCl)2 (5), 1,3‐C3H6(SCl)2 (6) or 1,2‐C6H4(SCl)2 (7), the bi‐ or monocyclic tetrakisdisulfanes C6H8S8 (9b), C8H12S8 (10), and C14H8S8 (11), respectively, were obtained. The X‐ray crystal structure analysis of 11 · CS2 showed that 11 possesses Ci symmetry with a central exocyclic CC double bond similar to tetrathiafulvalenes: C6H4(μ‐S2)2CC(μ‐S2)2C6H4.
Synthesis and Crystal and Molecular Structure of Tris(dimethylphenylsilyl)antimony
Authors: Sladek Alexander , Schmidbaur Hubert 
Published: July 2007

AbstractTris(dimethylphenylsilyl)antimony (1) was prepared in moderate yield from dimetallic “Na3Sb” (generated in situ) and chlorodimethylphenylsilane in tetrahydrofuran at reflux temperature. The product was identified by standard analytical and spectroscopic techniques, and the crystal structure was determined by single‐crystal X‐ray diffraction (triclinic, space group P1, Z = 2). The SbSi3 skeleton is pyramidal (average Si‐Sb‐Si angle 100.2°, average Sb‐Si bond length 2.558 Å), and the Me2PhSi groups are in a staggered conformation.
Soluble Substituted μ‐Oxo(phthalocyaninato)iron(III) Dimers
Authors: Dieing Reinhold , Schmid Gabriele , Witke Elisabeth , Feucht Carola , Dreßen Michael , Pohmer Jörg , Hanack Michael 
Published: July 2007

AbstractAttempts to prepare various peripheral tetra‐ and octasubstituted (phthalocyaninato)iron derivatives RnPcFe [n = 4: R = CH2OEt (6e), CO2Et (6h), CO2‐n‐C6H13 (6l), O(2‐Et‐n‐C6H13) (6j), OCH2C(CH3)3 (6k), OCH2C(CH3)2CH2Ph (6l); n = 8: R = CH2CH(CO2Me)CH(CO2Me)CH2 (6f), CH2CH(CO2Et)‐CH(CO2Et)CH2 (6g), O‐n‐C8H17 (6m), O(2‐Et‐n‐C6H13) (6n)] by starting from the corresponding substituted phthalonitriles led to substituted (μ‐oxo)bis[(phthalocyaninato)iron(III)] compounds [RnPcFe]2O. The tert‐butyl‐ and ethyl‐substituted systems [tBu4PcFe]2O (6c) and [Et4PcFe]2O (6d) were reinve‐stigated. UV/Vis, FD mass, Mössbauer, NMR as well as ESR spectroscopy was used to characterize the complexes [RnPcFe]2O to furnish evidence for the presence of Fe‐O‐Fe moieties in [RnPcFe]2O. The UV/Vis data reported for [RnPcFe]2O as well as their spectral behavior in pyridine correspond to unsubstituted [PcFe]2O. Mössbauer spectra of [RnPcFe]2O show that the complexes were obtained as a mixture of two isomeric μ‐oxo compounds A (δFe = 0.22 mm s‐1, ΔEQ = 1.33–1.39 mm s‐1) and B (ΔFe = 0.33–0.36 mm s‐1, ΔEQ = 0.39–0.53 mm s‐1), whose Mössbauer parameters are comparable to [PcFe]2O μ‐oxo(2) and μ‐oxo(1), respectively. Mössbauer spectral data of [RnPcFe]2O indicate high‐spin (S = 5/2) FeIII centers. NMR‐spectra of [RnPcFe]2O (n = 4: R = tBu, Et, O(2‐Et‐n‐C6H13), OCH2C(CH3)2CH2Ph; n = 8: R = O‐n‐C8H17, O(2‐Et‐n‐C6H13) give further evidence for μ‐oxo bridged structures.
Syntheses, Structures, and Equilibria of o‐, m‐, p‐Tolyl‐ and Phenylantimony Rings
Authors: Breunig Hans Joachim , Ebert Klaus Heinz , Gülec Sabahittin , Probst Joachim 
Published: July 2007

AbstractExchange reactions of R3Sb (R = o‐Tol, m‐Tol, p‐Tol) with SbCl3 in a 1:2 molar ratio give RSbCl2. Silylstibanes RSb(SiMe3)2 were obtained by reaction of RSbCl2 and Me3SiCl with Mg in THF. Slow access of air to solutions of RSb(SiMe3)2 afforded orange crystals of the composition (RSb)n. Crystal structures were determined by X‐ray crystallography for R = o‐Tol and m‐Tol as stacks of (RSb)6 rings in the chair conformation with equatorial substituents. In the crystals of (m‐TolSb)6 there are short intermolecular Sbb distances of 420 pm. Solutions of (RSb)n (R = Ph, o‐Tol, m‐Tol, p‐Tol) in C6D6 were analyzed by 1H‐NMR spectroscopy. They contain (RSb)5 and (RSb)4 in equilibria. Raman spectra of (PhSb)6 or (p‐TolSb)n show signals for Sbn at β = 151 or 153 cm‐1. 13C‐CP‐MAS‐NMR data of (p‐TolSb)n are reported.