bluuebunny/crossref_metadata_2025_split huggingface dataset:
Die Kuppel der Frauenkirche
Authors: Frenzel Christoph , Jäger Wolfram 
Published: June 2004

AbstractHeute wird das Stadtbild von Dresden wieder durch die sich aus ihm heraus erhebende Kuppel der Frauenkirche geprägt. Etwas mehr als 59 Jahre mußten vergehen, bis sie nach ihrer sinnlosen Zerstörung wiedererstanden ist. Architektonisch stellt sie ebenso wie konstruktiv eine herausragende Leistung des bürgerlichen Barocks dar. Ihre originale Rekonstruktion nach baumeisterlichen Prinzipien war eine Herausforderung und Verpflichtung für die beauftragten Architekten und Ingenieure.
Von der architektonischen Rekonstruktion zur Werkplanung
Authors: Frenzel Christoph 
Published: June 2004

AbstractDie Kuppel der Frauenkirche war Teil des von ihrem Erbauer George Bähr interpretierten, zeitgemäßen protestantischen Kirchenbauverständnisses und wurde aus diesem heraus von ihm entwickelt. Ihre architektonische Gestalt steht im Spannungsfeld zwischen äußerer Erscheinung und innerer Wirkung. Die Kühnheit der Gesamtkonstruktion verlangt im Vergleich mit andern Kuppeln Bewunderung. Im Original vorhandene Probleme machten behutsame Veränderungen notwendig. Die Rekonstruktion der Steinkuppel erforderte ein komplexes Herangehen an Architektur, Funktion und Konstruktion. Ausgestattet mit einer breiten, aber teilweise nur bedingt verwendbaren Quellenlage ist es gelungen, den hohen Ansprüchen an eine werkgerechte Wiedererrichtung der Frauenkirche und ihrer Kuppel architektonisch, steintechnisch und konstruktiv zu entsprechen.
Die Steintechnische Planung
Authors: Thomschke Matthias 
Published: June 2004

Abstract1995 erhielten die Sächsischen SANDSTEINWERKE erstmals den Auftrag zur Herstellung und Lieferung von Werksteinen für die Dresdner Frauenkirche. Seither begleiteten sie damit das Vorhaben bis hin zum letzten Stein, der in der Laterne am 13. April 2004 versetzt wurde. Zu Beginn der Arbeiten konnten Unternehmensleitung und Mitarbeiter noch nicht einschätzen, und so ging es vielen die am Wiederaufbau beteiligt waren, mit welchen Aufgaben sie in der Folgezeit konfrontiert werden sollten. Die fortschreitende Planung ging mit einer Fortbildung der einzelnen Bearbeiter wie auch des Unternehmens einher. Aus heutiger Sicht erscheint vieles, was geschaffen wurde, selbstverständlich. Die Lösungen von Problemen und komplizierten Aufgaben stellen sich heute logisch und einfach dar. Die vielen Stunden des Suchens vor der Lösung sind vergessen. Wenn Bauleute, Architekten und interessierte Menschen in einem Rundgang durch die Frauenkirche geführt werden und von der Arbeit berichtet wird, hört und spürt man immer wieder, welche Achtung allen am Wiederaufbau Beteiligten entgegengebracht wird.Nachfolgend wird ein Einblick in die schwierige Aufgabe der Erarbeitung der steintechnischen Angaben und Unterlagen für die Bearbeitung von Werksteinen allgemein als auch speziell für die Wiederherstellung der Kuppel gegeben.
Grundsätze der Bemessung und Konstruktion beim Wiederaufbau der Frauenkirche Dresden
Authors: Wenzel Fritz , Jäger Wolfram 
Published: June 2004

AbstractDen Leitlinien der Stiftung Frauenkirche folgend sollte das Bauwerk nach archäologischen Prinzipien und erneut in Stein, Mörtel und Eisen (Stahl) unter Verwendung von Originalmaterial aus dem Trümmerberg und Einbindung der Ruinenteile nach baumeisterlichen Prinzipien wieder aufgebaut werden. Angesichts der aus der Geschichte bekannten Schäden war das eine Herausforderung für die mit der Tragwerksplanung beauftragten Ingenieure, da es in den zurückliegenden Jahrzehnten keine Weiterentwicklung des Mauerwerks unter Einsatz von Naturstein für derart hoch beanspruchte Bauwerke und Bauteile gegeben hat. Der Beitrag gibt einen kurzen Überblick über den dabei eingeschlagenen Weg und die Grundlagen der Bemessung und Konstruktion des eingesetzten Ingenieurmauerwerks.
Die Gewölbe des Hauptbaus und die Innenkuppel
Authors: Hauer Markus , Stoll Volker 
Published: June 2004

AbstractZum Zeitpunkt der Errichtung der Frauenkirche George Bährs wurden obere Raumabschlüsse und zugleich die Schaffung horizontaler Ebenen ausschließlich durch Herstellung von Gewölben realisiert. Innerhalb der Frauenkirche sind damals verschiedenste Formen von Gewölben ausgeführt worden. Beim Wiederaufbau wurden diese Gewölbe in originalgetreuer Geometrie rekonstruiert. Wie vor 250 Jahren ist das mit Sandstein, Ziegeln und Mörtel erfolgt. In der Regel wurde dabei für Gewölbe, die mehr als ihr Eigengewicht abtragen, Sandsteinmauerwerk verwendet; ansonsten kam kleinformatiges Vollziegelmauerwerk zum Einsatz. Aufgrund der Vielzahl der beim Wiederaufbau ausgeführten Gewölbe kann der Beitrag nur einen Einblick in die Thematik geben. Es werden zwei besonders interessante Gewölbe ausführlich sowie die Innenkuppel kurz dargestellt.
Proliferation patterns of cervical cells as visualized in Leiden liquid cytology slides
Authors: Luzzatto Laura , van Haaften Carolien , Boon Mathilde E. 
Published: June 2004

AbstractThe Leiden liquid‐based cytology method for the preparation of optimal cytological slides is reported. In such slides, the proliferation pattern of cervical cells can be visualized in detail. Cervical smears and suspension preparations of 665 consecutive unselected patients received in 2003 were studied. Of the 665 patients, 26 (10 normal, 10 with cervical atrophy, 5 with mild dysplasia, and 1 carcinoma in situ) were selected. After using the Thermo Shandon Papspin, the wet slides were placed on a hot plate and dried for 30 min. Proliferation of the cervical cells was visualized in brown by staining the cells for MiB‐1 antigen, and nuclear DNA in blue by a standardized short staining with hematoxylin. We found excellent high‐resolution demonstrability of cell cycle‐related MiB‐1 distribution in the well‐flattened nuclei. The phase of the cell cycle could be deduced from brown‐blue staining patterns. There was a significant increase of MiB‐1‐positive cell yield related to progression in the degree of pathology. Diagn. Cytopathol. 2004;31:5–9. © 2004 Wiley‐Liss, Inc.
Aspiration cytology of sarcomatoid carcinoma of the breast: Report of a case with cystic change
Authors: Matthai Smita Mary , Kini Usha 
Published: June 2004

AbstractSarcomatoid/metaplastic carcinomas of the breast are rare breast malignancies that show a myriad of cytohistologic patterns in aspirates. These poorly differentiated invasive carcinomas contain both ductal and mesenchymal elements with transitional forms displaying either spindle, squamous, chondroid, or osseous differentiation. We describe such a neoplasm in a 68‐yr‐old woman, the diagnosis of which was missed at the initial fine‐needle aspiration (FNA) due to cystic change. Extensive cystic change in a sarcomatoid carcinoma is unusual and is reported for the first time in the English literature. Diagn. Cytopathol. 2004;31:10–13. © 2004 Wiley‐Liss, Inc.
Can cytomorphology differentiate between benign nodules and tumors arising in Graves' disease?
Authors: Anderson Scott R. , Mandel Susan , LiVolsi Virginia A. , Gupta Prabodh K. , Baloch Zubair W. 
Published: June 2004

AbstractFine‐needle aspiration (FNA) specimens from thyroid nodules arising in Graves' disease (GD) can pose diagnostic difficulties because the cytomorphologic changes in GD may mimic nuclear features of papillary thyroid carcinoma (PTC). In addition, treatment of GD patients with radioactive iodine (RAI) may cause significant cytologic atypia, further increasing the diagnostic difficulty. From March 1999 to April 2002, a total of 14 hypofunctioning nodules in 9 patients with GD underwent FNA; 3 patients had received RAI treatment. Three cases were diagnosed as suspicious for PTC and 11 as benign. Three patients with the diagnosis of suspicious for PTC on FNA underwent surgery and were found to have papillary carcinoma. We assessed all cases to find key cytologic features that can differentiate between nodules with reactive/reparative nuclear atypia from PTC arising in GD. The cytologic features assessed included cellularity, amount of colloid, monotony of the cell population, oncocytic features, cell crowding, lymphocytic infiltration, nuclear elongation, nuclear grooves, pale powdery chromatin, presence of small eccentric nucleoli, and random nuclear atypia. Each feature was semiquantitatively graded on a sliding scale of 0 to 4, with 0 representing absence and 4 representing a predominance of the feature. The mean value of each feature was calculated and the benign and malignant lesions were compared using the unpaired t‐test. Four features were found to be statistically significant in the diagnosis of PTC as compared to the benign nodules in GD. The nuclei of PTC in GD show prominent nuclear elongation, pale powdery chromatin, intranuclear grooves, and small eccentric nucleoli. All other features studied were not found to be statistically significant. There does exist an overlap between the cytologic features of benign nodules and PTC arising in GD. However, adherence to strict diagnostic criteria (nuclear elongation, pale powdery chromatin, intranuclear grooves, and small eccentric nucleoli) can enable the diagnosis of PTC arising in GD. Diagn. Cytopathol. 2004;31:64–67. © 2004 Wiley‐Liss, Inc.
Diagnostic impact of core‐needle biopsy on fine‐needle aspiration of non‐Hodgkin lymphoma
Authors: Gong Jerald Z. , Snyder Matthew J. , Lagoo Anand S. , Vollmer Robin T. , Dash Raj R. , Madden John F. , Buckley Patrick J. , Jones Claudia K. 
Published: June 2004

AbstractWe retrospectively reviewed 74 fine‐needle aspiration (FNA) cases of presumptive non‐Hodgkin lymphoma (NHL). All the cases had cytology and core‐needle biopsy and 53 cases had concurrent flow cytometric analysis. FNA (cytology and flow cytometry) and core‐needle biopsy were evaluated independently. FNA was diagnostic of diffuse large B‐cell lymphoma (DLBL) in 25% (13/53) of cases and small B‐cell NHL in 15% (8/53) of cases, whereas core‐needle biopsy was diagnostic of DLBL in 37% (27/74) of cases and small B‐cell NHL in 8% (6/74) of cases. Subclassification of small B‐cell NHL was reached in 3/6 cases by core‐needle biopsy. Insufficient cases were observed in both FNA (47%; 25/53) and core‐needle biopsy (28%; 21/74) groups. With the combination of FNA and core‐needle biopsy, diagnostic cases of DLBL increased to 43% (32/74) and insufficient samples were reduced to 16% (12/74). There was no clear advantage in the diagnosis and classification of small B‐cell NHL by adding core‐needle biopsy to FNA (14%; 10/74). We conclude that core‐needle biopsy is a useful adjunct to FNA in the diagnosis of DLBL and shall be encouraged. In small B‐cell NHL, core‐needle biopsy does not add to the diagnostic ability of FNA. Cases insufficient for diagnosis may be seen in both core‐needle biopsy and FNA. A combined approach reduces the number of insufficient cases and is recommended in routine FNA practice. Diagn. Cytopathol. 2004;31:23–30. © 2004 Wiley‐Liss, Inc.
Thyroid low‐grade B‐cell lymphoma (MALT type) with extreme plasmacytic differentiation: Report of a case diagnosed by fine‐needle aspiration and flow cytometric study
Authors: Al‐Marzooq Yusef M. , Chopra Rajan , Younis Mohammed , Al‐Mulhim Abdulrahman S. , Al‐Mommatten Mohammed I. , Al‐Omran Soad H. 
Published: June 2004

AbstractWe describe a case of thyroid marginal‐zone B‐cell lymphoma of mucosa‐associated lymphoid tissue (MALT lymphoma) with extreme plasmacytic differentiation in an 80‐year‐old woman who had presented with a rapidly growing thyroid swelling. The diagnosis was initially suspected on fine‐needle aspiration (FNA) and subsequently confirmed by flow cytometric analysis of the aspirated material. The smears revealed features of Hashimoto's thyroiditis admixed with large numbers of atypical large plasmacytoid lymphoid cells accompanied by variable numbers of small lymphocytes and mature plasma cells. The differential diagnosis of a predominantly plasmacytic smears on FNA of the thyroid is discussed herein, with emphasis on the role of immunophenotypic studies to exclude or confirm the diagnosis of lymphoma. Diagn. Cytopathol. 2004;31:52–56. © 2004 Wiley‐Liss, Inc.
Extracellular material in adenoid cystic carcinoma of the salivary glands: A comparative cytological study with other salivary myoepithelial tumors
Authors: Kawahara Akihiko , Harada Hiroshi , Kage Masayoshi , Yokoyama Toshiro , Kojiro Masamichi 
Published: June 2004

AbstractThe objective of this study was to clarify extracellular materials (ECMs) in adenoid cystic carcinoma (AdCC) and compare these to those found in other salivary gland tumors with myoepithelial differentiation. The ECM was examined with Papanicolaou, May‐Grünwald‐Giemsa (MGG), and alcian blue stain at pH 2.5. The ECM in AdCC was classified into three types according to their staining patterns: clear, hyalinized, and membrane type. The incidence of clear‐type globule material with magenta on MGG was low in other salivary gland tumors with myoepithelial differentiation. The ECM was identified in other salivary gland tumors with myoepithelial differentiation. However, AdCC has the greatest variety of ECM. These findings are useful to understand the character of AdCC and differential diagnosis of the other salivary gland tumors with myoepithelial differentiation. Diagn. Cytopathol. 2004;31:14–18. © 2004 Wiley‐Liss, Inc.
Fine‐needle aspiration cytology of endometrioid adenofibroma of the ovary
Authors: Volmar Keith E. , Herman Christopher M. , Creager Andrew J. 
Published: June 2004

AbstractWe report the fine‐needle aspiration (FNA) cytology findings of endometrioid adenofibroma arising in the ovary of a 60‐year‐old woman who presented with vaginal bleeding. Imaging studies revealed a large pelvic mass, which was sampled by computed tomography‐guided FNA and core biopsy. The FNA yielded cellular smears composed of bland endometrioid cells and fragments of ovarian‐type stroma. The core biopsy showed a biphasic process comprising bland endometrioid glands in a spindle‐cell stroma. Immunohistochemical studies performed on the core showed the stroma to be CD10‐negative and smooth muscle actin‐positive. Subsequent resection of the tumor confirmed the diagnosis and revealed an adenocarcinoma arising in the tumor that was not sampled by FNA. To our knowledge, the cytologic features of ovarian endometrioid adenofibroma have not been previously described. Diagn. Cytopathol. 2004;31:38–42. © 2004 Wiley‐Liss, Inc.
The η5‐(σ‐P,π‐Arene) Chelating H‐MOP Ligand in an Optically and Catalytically Active Rhodium(I) Complex
Authors: Soleilhavoup Michèle , Viau Lydie , Commenges Gérard , Lepetit Christine , Chauvin Remi 
Published: June 2004

Abstract(R)‐methylbinapium, a Hayashi‐type phosphonium‐MOP ligand, reacts with [Rh(cod)2][BF4] in ethanol to afford the chiral mixed bis(monophosphane)rhodium(I) complex [Rh(η5‐H‐MOP)(MePh2P)][BF4]. The constitutional and geometrical features of this complex have been determined by exhaustive 1H, 11B, 13C, 31P and 103Rh 1‐D, 2‐D and NOE NMR spectroscopy and optical rotation measurements. The chelating η5‐(γ‐phosphanyldiene) ligand character of H‐MOP in this complex is an extension to RhI of similar coordination modes studied by Pregosin in the coordination sphere of RuII. The process of its formation relies on an enantiospecific reductive cleavage of a P+−C bond, which is also reminiscent of Pregosin’s P−C bond cleavages in the ruthenium series. The complex is a catalytic precursor for the hydrogenation of (Z)‐α‐acetamidocinnamic acid. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Gold(I) Macrocycles and [2]Catenanes Containing Sulfone‐Functionalised Diacetylide Ligands
Authors: Mohr Fabian , Jennings Michael C. , Puddephatt Richard J. 
Published: June 2004

AbstractThe reaction of the polymeric digold(I) diacetylide [(AuCCCH2OC6H4)2SO2]n with diphosphane ligands PP leads to the formation of either macrocyclic ring complexes [(AuCCCH2OC6H4)2SO2(μ‐PP)] or [2]catenanes [(AuCCCH2OC6H4)2SO2(μ‐PP)]2 by a self‐assembly process. With the diphosphane ligands Ph2PCCPPh2, [Fe(C5H4PPh2)2] and Ph2P(CH2)nPPh2 (n = 4, 5 and 6), macrocyclic ring complexes result, but with the diphosphane ligand Ph2P(CH2)3PPh2, the [2]catenane selectively crystallises from an isomeric mixture of products. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Dynamic Properties of Methyl(trimethylphosphane)nickel Complexes Containing (2‐Diphenylphosphanyl)phenylamido Ligands
Authors: Klein Hans‐Friedrich , Beck Robert , Hetche Olaf 
Published: June 2004

AbstractP,N‐chelates of nickel NiCl[2‐(Ph2P)C6H4NR](PMe3) (1: R = H; 2: R = SiMe3) have been obtained from NiCl2(PMe3)2 and 2‐(Ph2P)C6H4NRLi. Reaction with MeLi affords methylnickel compounds NiMe[2‐(Ph2P)C6H4NR](PMe3) (3: R = H; 4: R = Me; 5: R = SiMe3). By the same route NiMe[2‐(R1R2P)C6H4NR](PMe3) (6: R1 = R2 = CHMe2) was synthesized. Solutions in THF contain cis and trans isomers of square‐planar complexes, and dynamic NMR spectroscopy shows dissociation of trimethylphosphane to be more rapid in the trans isomers. In a crystal of 5 the molecular structure is cis‐5. Out of these complexes only 3 and 4 add trimethylphosphane to form pentacoordinate compounds NiMe[2‐(Ph2P)C6H4NR](PMe3)2 (7, 8) in the crystal as shown by the molecular structure of 7 while in THF equilibria 7 ⇄ cis‐1 and 8 ⇄ cis‐2 are observed by NMR spectroscopy. The same solution properties are found with NiMe[2‐(R1R2P)C6H4NR](PMe3)2 (9: R1 = CMe3, R2 = Ph). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Fluxional and Rigid (Trimethylphosphane)cobalt Complexes Containing Chelating (2‐Diphenylphosphanyl)anilido Ligands
Authors: Klein Hans‐Friedrich , Beck Robert , Flörke Ulrich , Haupt Hans‐Jürgen 
Published: June 2004

Abstract2‐(Diphenylphosphanyl)anilines (P∧NHR) eliminate methane upon reaction with [CoMe(PMe3)4] forming the complexes [Co(η2‐P∧NR)(PMe3)3] (1: R = H; 2: R = Me) and [Co(η2‐P∧NR)(PMe3)2] (3: R = Me). Reaction with HCl gives [CoCl(η1‐P∧NHR)(PMe3)2] (4: R = H; 5: R = Me) and reaction with CO or olefin gives [Co(η2‐P∧NR)(CO)(PMe3)2] (6: R = H; 7: R = Me) and [Co(η2‐P∧NR)(olefin)(PMe3)2] (8: R = H, olefin = C2H4; 9: R = Me, olefin = C2H4; 10: R = Me, olefin = C3H6), respectively. No catalytic transformation of the olefins was observed. Oxidation by iodomethane yields a cobalt(II) compound [CoI(η2‐P∧NR)(PMe3)2] (11: R = Me). By treating 2‐(diphenylphosphanyl)aniline with [CoMe2(PMe3)3] a methylcobalt(II) complex [CoMe(η2‐P∧NR)(PMe3)2] (12: R = H) is obtained, while an excess of the aniline produces [Co(η2‐P∧NR)2] (13: R = H; 14: R = Me) or [Co(η2‐P∧NR)2(PMe3)] (15: R = H; 16: R = Me). The methylcobalt(III) complexes mer‐trans‐[CoIMe2(η2‐P∧NR)(PMe3)2] were obtained from LiP∧NR and [CoClMe2(PMe3)3]. Dynamic 31P NMR spectra and the structures of complexes 3, 6, 12, and 13 are discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthesis, Crystal Structure, and Photoluminescent Properties of a Tetracarbonyl(naphthyridylcarbamoyl)rhenium(I) Complex and a Highly Emissive Tetracarbonyl(naphthyridylamido)rhenium(I) Complex
Authors: Zuo Jing‐Lin , Fu Wen‐Fu , Che Chi‐Ming , Cheung Kung‐Kai 
Published: June 2004

AbstractThe reactions of Re(CO)5X (X = Cl, Br) with 7‐amino‐2,4‐dimethyl‐1,8‐naphthyridine (H2L1) and 7‐[2‐(6‐chloropyridyl)amino]‐2,4‐dimethyl‐1,8‐naphthyridine (HL2) in the presence of tBuOK afforded the η1‐naphthyridylcarbamoyl complex [Re(CO)4(HL1CO)] (1) and the naphthyridylamido complex [Re(CO)4(L2)] (2), respectively. The structures of HL2, 1·CHCl3, 1·HL3·2CH2Cl2 [HL3 = (7‐chloronaphthyridyl)(5,7‐dimethylnaphthyridyl)amine], and 2 have been determined by X‐ray crystallography. Complex 1 displays a weak emission at 453 nm in an EtOH/MeOH (1:4, v/v) glassy solution at 77 K; complex 2 exhibits an intense (quantum yield: 0.22 in CH2Cl2) and long‐lived emission (46 μs in CH2Cl2), with a solvent‐sensitive λmax, in degassed solutions at room temperature. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2003)
Synthesis, Spectra and Crystal Structure of Two Copper(I) Complexes of Acetonethiosemicarbazone
Authors: Lhuachan Sanchai , Siripaisarnpipat Sutatip , Chaichit Narongsak 
Published: June 2004

AbstractThe reaction of copper(I) chloride with acetonethiosemicarbazone (tscac) in a copper to tscac molar ratio of 1:2 forms the cationic complex [Cu(tscac)2]Cl (1). When the ratio of the copper to tscac was reduced to 1:1, a dimeric complex [Cu2Cl2(tscac)2]2 (2) was obtained. In complex 2, two CuCl2 species act as bridging groups between two Cu(tscac)2 moieties forming an eight‐membered ring, whereas in complex 1, there is no CuCl2 moiety in the structure. In both complexes the copper(I) center is coordinated in a distorted tetrahedral geometry to two tscac groups through the sulfur and the imine nitrogen atom. In dimeric complex 2, the sulfur atom in each tscac ligand coordinates weakly to copper(I) in the CuCl2 moiety giving the distorted tetrahedral geometry. For the free ligand, the νc=s vibration at 789 cm−1 appears at lower energy than in complexes 1 and 2 (754 and 744 cm−1 respectively) indicating coordination at the sulfur atom. The complexes synthesized by either electrochemical or chemical methods are identical. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Thermodynamic and Kinetic Data for the Base‐On/Base‐Off Equilibration of Alkylcobalamins
Authors: Hamza Mohamed S. A. , Zou Xiang , Brown Kenneth L. , Eldik Rudi van 
Published: June 2004

AbstractThe base‐on/base‐off equilibration of a series of alkylcobalamins (XCbl) was studied as a function of the electronic properties of X. A square scheme was developed to incorporate all species that participate in this equilibration. The equilibrium between five‐ and six‐coordinate species was studied for several alkylcobalamins (protonated base‐off) and alkylcobinamides as a function of pressure by using UV/Vis spectroscopy. In addition, the kinetics of the acid‐induced base‐on/base‐off equilibration of β‐NCCH2Cbl, β‐CF3Cbl and CNCbl were studied; the data obtained reveal evidence for an acid‐catalysed reaction path. The results of this study and the observed correlations are discussed in reference to those reported in the past, and enable the formulation of an overall equilibration scheme. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Halogen Atoms as Reactive Centers for the Introduction of Functional Side Chains into (Arene)ruthenium(0) Complexes
Authors: Bodes Gregor , Heinemann Frank W. , Jobi Günter , Klodwig Jens , Neumann Stefan , Zenneck Ulrich 
Published: June 2004

AbstractSubstitution of the naphthalene ligand of [(COD)(η6‐naphthalene)Ru] (2) (COD = 1,5‐cyclooctadiene) by suitable haloarenes (halogen = F, Cl, Br, I) affords several new mono‐ and dihaloarene(cyclooctadiene)ruthenium complexes. Depending on the number and position of the halogen and organyl substituents, the haloarenes form achiral or planar‐chiral π‐ligands; [(η6‐bromoarene)(COD)Ru] complexes are prone to rapid bromine/lithium exchange with nBuLi at low temperatures, while the chloro and fluoro derivatives undergo ortho‐metalation under the same conditions. The lithiated species react readily with chiral or achiral electrophiles such as chlorodiorganophosphanes, carbonyl chlorides, aldehydes, lactones, ketones, and epoxides to yield substituted [(η6‐arene)(COD)Ru] complexes with donor functions in their side chains, inaccessible by other routes. Enantiopure complexes are obtained when achiral lithioarene complexes are combined with chiral electrophiles, but pairs of diastereomers are formed if the lithioarene ligand is a planar‐chiral species. Dinuclear ruthenium complexes [1,1‐bis{(COD)(η6‐phenyl)Ru}‐1,4‐butanediol] (28) and [1,1‐bis{(COD)(η6‐4‐fluorophenyl)Ru}‐1,4‐butanediol] (30) with two (η6‐aryl)(COD)Ru units linked by a common 1,4‐butanediol side chain are formed through the reactions between the appropriate lithioarene complexes and γ‐butyrolactone. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2003)