bluuebunny/crossref_metadata_2025 huggingface dataset:
The safety of interferon‐γ‐1b therapy for invasive fungal infections after hematopoietic stem cell transplantation
Authors: Safdar Amar , Rodriguez Gilhen , Ohmagari Norio , Kontoyiannis Dimitrios P. , Rolston Kenneth V. , Raad Issam I. , Champlin Richard E.
Published: January 2005

BACKGROUND

The restoration of normal immune responses, especially of the T‐helper type 1 immune response, is an important predictor of fungal infection outcome in patients with malignant disease who undergo hematopoietic stem cell transplantation (HSCT). The authors sought to evaluate the safety of adjuvant recombinant interferon‐γ‐1b as an immune‐modulatory therapy HSCT recipients.

METHODS

Thirty‐two patients received interferon‐γ‐1b after undergoing HSCT at the author's institution between 1998 and 2003. A retrospective analysis was undertaken after obtaining permission from the Institutional Review Board.

RESULTS

Twenty‐six of 32 patients (81%) received allogeneic stem cell grafts. All but 1 patient received interferon‐γ‐1b and antifungals to treat infections; the other patients received interferon‐γ‐1b to promote autologous graft‐versus‐tumor effect. Interferon‐γ‐1b usually was administered at a dose of 50 μg subcutaneously every other day. The median duration (± standard deviation) of interferon‐γ‐1b therapy was 6 ± 6.5 doses (range, 1–29 doses), and the median cumulative dose was 487 ± 453 μg (range, 35–2175 μg). During therapy with interferon‐γ‐1b, fever was common (n = 9 patients; 28%). In 1 patient (3%), new‐onset lymphocytopenia occurred but resolved after cytokine therapy was discontinued; there were no interferon— γ‐1b‐related episodes of neutropenia, thrombocytopenia, anemia, or liver dysfunction. Interferon‐γ‐1b therapy did not precipitate or exacerbate acute or chronic graft‐versus‐host disease (GVHD). In fact, in 2 of 7 patients (29%) with acute GVHD and in 3 of 10 patients (30%) with chronic GVHD, significant improvements in GVHD were noted during therapy with interferon‐γ‐1b. Among the 26 patients with aspergillosis, 14 patients (54%) died. However, 5 of 10 patients (50%) with presumed pulmonary aspergillosis, 3 of 9 patients (33%) with probable pulmonary aspergillosis, 1 of 2 patients (50%) with definite pulmonary aspergillosis, and 3 of 5 patients (60%) with disseminated aspergillosis responded to antifungals and adjuvant interferon‐γ‐1b.

CONCLUSIONS

Recombinant interferon‐γ‐1b was tolerated without serious adverse reactions in HSCT recipients. A large, prospective, randomized study will be needed to evaluate the efficacy of this cytokine in high‐risk HSCT recipients who have invasive mycoses. Cancer 2005. © 2005 American Cancer Society.
A New Heptanuclear Dendritic Ruthenium(II) Complex Featuring Photoinduced Energy Transfer Across High‐Energy Subunits
Authors: Puntoriero Fausto , Serroni Scolastica , Galletta Maurilio , Juris Alberto , Licciardello Antonino , Chiorboli Claudio , Campagna Sebastiano , Scandola Franco
Published: January 2005

The new heptanuclear ruthenium(II) dendron, [Cl2Ru{(μ‐2,3‐dpp)Ru[(μ‐2,3‐dpp)Ru(bpy)2]2}2](PF6)12 (1; 2,3‐dpp=2,3‐bis(2′‐pyridyl)pyrazine; bpy=2,2′‐bipyridine), was prepared by means of the “complexes as ligands/complexes as metals” synthetic strategy, and its absorption spectrum, redox behavior, and luminescence properties were investigated. Compound 1 is a multicomponent species, which contains three different types of chromophores (namely, the {Cl2Ru(μ‐2,3‐dpp)2} core, the {Ru(μ‐2,3‐dpp)3}2+ intermediate, and the {(bpy)2Ru(μ‐2,3‐dpp)}2+ peripheral subunits) and several redox‐active sites. The new species exhibits very intense absorption bands in the UV region (ε value in the 105–106 M−1 cm−1 range) as a result of spin‐allowed ligand‐centered (LC) transitions, and intense bands in the visible region (ε value in the 104–105 M−1 cm−1 range) as a result of the various spin‐allowed metal‐to‐ligand charge‐transfer (MLCT) transitions. The redox investigation (accomplished by cyclic and differential pulse voltammetry) indicates that 1 undergoes a series of reversible metal‐centered oxidation and ligand‐centered reduction processes within the potential window investigated (+1.90/−1.40 V vs. the standard calomel electrode, SCE). The assignment of each absorption band and redox process to specific subunits of 1 was achieved by comparison with the properties of smaller multinuclear species of the same family, namely [Cl2Ru{(μ‐2,3‐dpp)Ru(bpy)2}2]4+ (2), [(bpy)2Ru(μ‐2,3‐dpp)Ru(bpy)2]4+ (4), and [Ru{(μ‐2,3‐dpp)Ru(bpy)2}3]4+ (5). The title compound exhibits luminescence both at room temperature in acetonitrile fluid solution and at 77 K in butyronitrile rigid matrix. The emission is attributed to the triplet MLCT (3MLCT) state involving the core {Cl2Ru(μ‐2,3‐dpp)2} subunit. Interestingly, the 3MLCT levels involving the peripheral {(bpy)2Ru(μ‐2,3‐dpp)}2+ subunits are deactivated by energy transfer to the emitting level, in spite of the presence of interposed high‐energy {Ru(μ‐2,3‐dpp)3}2+ components, which, in other dendrimers, acted as “isolating” subunits toward energy‐transfer processes. Ultrafast experiments on 1 and on the parent species 2 and 5 allowed us to rationalize this behavior and highlight that a sequential two‐step electron‐transfer process can be held responsible for the efficient overall energy transfer, which offers a way to overcome a limitation in antenna metal dendrimers.
Cover Picture: Direct Visualization of Lipid Phase Segregation in Single Lipid Bilayers with Coherent Anti‐Stokes Raman Scattering Microscopy (ChemPhysChem 1/2005)
Authors: Potma Eric O. , Xie X. Sunney
Published: January 2005

The cover picture shows lipid phase segregation in a single giant unilamellar vesicle (GUV) visualized with coherent anti‐Stokes Raman scattering (CARS) microscopy. Phase segregation can be clearly observed, as is evidenced by the CARS image of the deuterated lipid (red) overlaid for clarity with the image of the undeuterated lipid (green). The high sensitivity of CARS microscopy allows visualization of the GUV single lipid bilayer when the Raman shift is tuned into the frequency of the symmetric stretching vibrational mode of CH2, which is abundant in lipid molecules. X. S. Xie et al. show in their Communication on page 77 that CARS microscopy opens up possibilities for intracellular studies of lipid domains.
The cytological spectrum of chronic pancreatitis
Authors: Stelow Edward B. , Bardales Ricardo H. , Lai Rebecca , Mallery Shawn , Linzie Bradley M. , Crary Gretchen S. , Stanley Michael W.
Published: January 2005

Chronic pancreatitis (CP) refers to a spectrum of changes generally seen after repeated injury that ranges histologically from mild fibrosis to extensive fibroinflammatory replacement of acinar tissue with accumulation of calcific debris. Because CP can share clinical and radiological features with malignancy, it often is sampled by fine‐needle aspiration (FNA). The cytology files at Hennepin County Medical Center (HCMC) were searched for 20 consecutive cases of CP sampled by FNA. Clinical data and cytological findings were recorded. A spectrum of cytological findings typifies aspirates of CP. In most cases, mixed inflammation with debris and calcific material is present. Often, ductal cells are present and at most show mild atypia but generally appear organized. Often, fibrotic acinar tissue also is present while definitive islets are identified only rarely. Although these cytological findings were consistent with CP, 3 of 17 patients with follow‐up were found to have pancreatic ductal adenocarcinoma. Diagn. Cytopathol. 2005;32:65–69. © 2005 Wiley‐Liss, Inc.
Bilateral primary lymphoma of the breast: A case report initially diagnosed by FNAC
Authors: Maounis N. , Ellina E. , Papadaki Th. , Ioannides G. , Kiale K. , Finokaliotis N. , Blana AiK.
Published: January 2005

Primary lymphoma of the breast (PLB) is a rare disease, representing 0.04–0.5% of all malignant breast neoplasms. We present a patient with bilateral breast involvement by a high‐grade diffuse large B‐cell lymphoma, which was diagnosed initially by fine‐needle aspiration cytology (FNAC). Mammography revealed a diffuse increase in density of the right breast and a large solitary mass on the left breast, suggestive of an inflammatory carcinoma. The patient underwent FNAC and the diagnosis of a non‐Hodgkin's lymphoma (NHL) was suggested. Physical examination revealed palpable bilateral axillary lymph nodes but no evidence of concurrent widespread disease. The patient underwent complete staging evaluation. The only positive findings were an elevated lactate dehydrogenase (LDH) and evidence of axillary lymphadenopathy on CT. Excisional biopsy was performed on the left breast. The morphological and immunohistochemical analysis confirmed the diagnosis of a high‐grade diffuse large B‐cell lymphoma with an immunophenotype suggestive of a germinal center cell origin. Diagn. Cytopathol. 2005;32:114–118. © 2005 Wiley‐Liss, Inc.
Differential expression of cdk inhibitors p16, p21cip1, p27kip1, and cyclin E in cervical cytological smears prepared by the ThinPrep method
Authors: Moore Grace D. , Lear Sheron C. , Wills‐Frank Lisa A. , Martin Alvin W. , Snyder James W. , Helm C. William
Published: January 2005

Our objective was to correlate p16, p21cip1, p27kip1, and cyclin E protein expression with the degree of dysplasia on ThinPrep Papanicolaou (Pap) smears using a modified immunoperoxidase staining. Smears read as normal, atypical squamous cells of undetermined significance (ASC‐US), low‐grade squamous intraepithelial lesion (LSIL), or high‐grade SIL (HSIL) were identified and tested for high‐risk human papillomavirus (HR‐HPV). Additional smears were processed for immunoperoxidase for p16, p21cip1, p27kip1, and cyclin E. Thirty‐four smears were satisfactory for study. The p16 was positive in all nine HSIL, in four of nine LSIL, and in one of seven ASC‐US. The p27kip1 was positive in all nine HSIL, in eight of nine LSIL, and in one of seven ASC‐US. The p21cip1 was positive in all nine HSIL, in one of nine LSIL, and in one of seven ASC‐US. Cyclin E was positive in seven of nine HSIL and in one of nine LSIL and in none of the ASC‐US smears. Normal smears were negative for all the antigens. There was poor correlation of protein expression and HR‐HPV infection. We concluded that p16, p21cip1, p27kip1, and cyclin E can be demonstrated on Pap smears and they are expressed differentially in dysplastic cells, with highest expression in HSIL. The p21cip1 and cyclin E showed the greatest correlation with HSIL. Diagn. Cytopathol. 2005;32:82–87. © 2005 Wiley‐Liss, Inc.
A cost‐effectiveness analysis of four management strategies in the determination and follow‐up of atypical squamous cells of undetermined significance
Authors: Hughes Alice A. , Glazner Judith , Barton Phoebe , Shlay Judith C.
Published: January 2005

Atypical squamous cells of undetermined significance (ASC‐US) are the most common abnormal cytological result on Papanicolaou (Pap) smear. We analyzed four management strategies in a hypothetical cohort of women divided by age group: (1) immediate colposcopy, (2) repeat cytology after an ASC‐US Pap smear result, (3) conventional Pap with reflex human papillomavirus (HPV) testing, and (4) liquid‐based cytology with reflex HPV testing. Parameter variables were collected from previously published data. Strategies that included reflex HPV testing had the lowest overall costs for all age groups combined. Repeat Pap smears had the highest number of true positive results throughout all stages but also had the uppermost number of missed cancers and highest costs. Immediate colposcopy had the second highest overall costs and detected fewer true positive results than liquid‐based cytology. Younger women (aged 18–24 yr) consistently had higher total costs for all strategies investigated. Using the incremental cost‐effectiveness (CE) ratio, the immediate colposcopy strategy was more costly and less effective than liquid‐based cytology and, therefore, was dominated. The incremental CE ratio was lowest for liquid‐based cytology compared with conventional cytology and liquid‐based cytology with reflex HPV testing was the most cost‐effective strategy. Diagn. Cytopathol. 2005;32:125–132. © 2005 Wiley‐Liss, Inc.
Generalized wall functions and their application for simulation of turbulent flows
Authors: Utyuzhnikov S. V.
Published: January 2005

Generalized wall functions in application to high‐Reynolds‐number turbulence models are derived. The wall functions are based on transfer of a boundary condition from a wall to some intermediate boundary near the wall (usually the first nearest to a wall mesh point but that is not obligatory). The boundary conditions on the intermediate boundary are of Robin‐type and represented in a differential form. The wall functions are obtained in an analytical easy‐to‐implement form, taking into account source terms such as pressure gradient, and do not include free parameters. The log‐profile assumption is not used in this approach. Although the generalized wall functions are obtained for the k–ε model, generalization to other turbulence models is straightforward. The general approach suggested can be applied for studying high‐temperature regimes with variable laminar viscosity and density. Copyright © 2005 John Wiley & Sons, Ltd.
Crystallographic analysis of thermochromic, unsolvated tetramesityldisilene at 173 K and 295 K
Authors: Shepherd Brian D. , Campana Charles F. , West Robert
Published: January 2005

X‐ray crystal structure determinations of tetramesityldisilene (1) at 295 K, where it is bright orange, and at 173 K, where it is pale yellow, were experimentally equivalent. The thermochromism of 1, therefore, is not due to changes in conformation; a vibrational origin is considered. The crystal structure of unsolvated 1 differs substantially from that of the toluene solvate (1·C7H8) because of different crystal packing of the two forms. These two solid‐state structures are compared with those of four other disilenes.
Asymmetric synthesis of tertiary alcohols from α‐halo boronic esters
Authors: Matteson Donald S. , Hurst Gerald D.
Published: January 2005

Reaction of pinanediol boronates with (1,1‐dichloroethyl)lithium generated in situ at −78°C followed by rearrangement of the resulting borate complex 2S in the presence of zinc chloride at 25°C has resulted in chirally biased insertion of the 1‐chloroethyl group into the carbon–boron bond. (s)‐Pinanediol phenylboronate (7) produced (s)‐pinanediol (1S)‐(1‐chloro‐1‐phenylethyl)boronate (8S) in 92% DE. Nonstererospecific reaction with ethylmagnesium bromide to form (s)‐pinanediol (1S)‐(1‐phenyl‐1‐methylpropyl)boronate (5S) reduced the DE to 88%. Peroxidic deboronation yielded (R)‐(+)‐2‐phenyl‐2‐butanol (6R) (84% EE). (s)‐Pinanediol ethylboronate (4) with (1,1‐dichloroethyl)lithium showed the opposite chiral preference, yielding (s)‐pinanediol (1R)‐(1‐chloro‐1‐methylpropyl)boronate (3R) (89% DE), which was converted by phenylmagnesium bromide followed by hydrogen peroxide to 6R (76% EE). Diastereoselections were small in reactions of (1,1‐dichloroethyl)‐lithium with n‐alkylboronates 9a and 13 and with cyclohexylboronate 9c. The 13 was converted to the enantiomer of the insect pheromone frontalin (17) (21% EE). Good diastereoselections were found with α‐substituted alkylboronates 9b and 18, but the configurations of the products could not be determined. (s)‐Pinanediol (1,1‐dichloroethyl)boronate (1) reacts with Grignard reagents via an intermediate borate 2R with negligible diastereoselection.
π‐Complexes of p‐block elements: (η6‐Mesitylene)tin(II) chloride tetrachloroaluminate(III), a coordination polymer
Authors: Schmidbaur Hubert , Probst Thomas , Steigelmann Oliver , Müller Gerhard
Published: January 2005

(η6‐1,3,5‐Trimethylbenzene)tin(II) chloride tetrachloroaluminate(III), (η6‐1,3,5‐C6H3Me3)SnCl (AlCl4), has been obtained from the reaction of anhydrous SnCl2 and AlCl3 in the molar ratio 1 : 2 in excess mesitylene as a solvent. The compound crystallizes in monoclinic needles, space group P21/n, containing a coordination polymer with planar four‐membered rings Sn‐Cl‐Sn‐Cl as the fundamental structural units. Each tin(II) atom of these rings is η6‐bonded to a mesitylene ring, with the metal approximately centered over the aromatic hydrocarbon at a distance of 2.71 Å. Each of the tin(II) atoms is further connected to two tetrachloroaluminate counter ions, one of these monodentate and one bidentate. Through this mono/bidentate contacts a one‐dimensional coordination polymer is generated with crystallographic centers of inversion in the middle of the Sn(Cl)2Sn and Sn(AlCl4)2Sn rings. The structure is similar to that of the analogous benzene complex, but not identical owing to a different connectivity pattern. Also, the arene‐Sn(II) distance is much shorter in the mesitylene complex (2.71 Å) than in the benzene complex (2.90 Å), indicating that the trimethylbenzene molecule is a much better donor than benzene.
1‐Phosphinodiazaphosphene: Synthesis, crystal structure, and bonding properties
Authors: Altmeyer Oliver , Niecke Edgar , Nieger Martin , Busch Thilo , Schoeller Wolfgang W. , Stalke Dietmar
Published: January 2005

The iminophosphane, tBu2PPNNR2 (RSiMe3), produced by base‐catalyzed elimination of ClSiMe3 from the corresponding phosphane, possesses an unusually long PN bond (162 pm), which is in accord with quantum chemical calculations.
Synthesis of S‐methylisoproylidenehydrazinecarbodithioate complexes of aluminim
Authors: Barron Andrew R. , Davies Geoffrey
Published: January 2005

Aluminum(III) complexes of S‐methylisopropylidenehydrazinecarbodithioate have been synthesized and characterized by 1H, 13C and 27Al NMR.
The preparation and characterization of binary phosphorus–selenium rings
Authors: Pilkington Mark J. , Slawin Alexandra M. Z. , Williams David J. , Wood Paul T. , Woollins J. Derek
Published: January 2005

Depending on the ratio of reactants, reaction of (PPh)5 (1) with grey selenium gives (PhPSe2)2 (2), (PhP)3Se2 (3), (PhP)4Se (4), and (PhP)3Se3 (5). The compounds have been characterized by multielement NMR, mass spectrometry, microanalyses, and, in the case of 4, X‐ray crystallography. 4 consists of a puckered 5‐membered ring with all four phenyl substituents axial; the average P–P and P–Se bond lengths are 2.194 and 2.271 Å respectively.
Synthesis of mesocyclic and macrocyclic polythioethers using the cesium dithiolate technique
Authors: Setzer William N. , Afshar Shahrara , Burns Norman L. , Ferrante Lucille A. , Hester Amy M. , Meehan Edward J. , Grant Gregory J. , Isaac Saju M. , Laudeman Christopher P. , Lewis Charles M. , VanDerveer Donald G.
Published: January 2005

The mesocyclic trithioethers, 1,4,7‐trithiacyclodecane, 1,4,7‐trithiacycloundecane, 1,4,8‐trithiacycloundecane, and 1,5,9‐trithiacyclododecane; the mesocyclic trithioether ketones, 1,4,7‐trithiacyclodecan‐9‐one; 1,4,8‐trithiacycloundecan‐6‐one, and 1,5,9‐trithiacyclododecan‐3‐one; and the mesocyclic trithioether alcohols, 1,4,7‐trithiacyclodecan‐9‐ol, 1,4,8‐trithiacycloundecan‐6‐ol, and 1,5,9‐trithiacyclododecan‐3‐ol, have been synthesized using the cesium dithiolate technique. In some cases, the corresponding macrocyclic hexathioether was isolated from the reaction mixture in addition to the mesocyclic trithioether; 1,4,7,11,14,17‐hexathiacycloeicosane, 1,4,7,11,14,17‐hexathiacycloeicosan‐9,19‐dione, 1,4,7,12,15,18‐hexathiacyclodocosane, and 1,5,9,13,17,21‐hexathiacyclotetracosane. Single‐crystal X‐ray structures have been determined for 1,5,9‐trithiacyclododecan‐3‐ol and 1,4,7,12,15,18‐hexathiacyclodocosane. For 1,5,9‐trithiacyclododecane‐3‐ol, the compound crystallizes in the monoclinic space group, C2/c, with a = 10.5926(9) Å, b = 15.582(2) Å, c = 13.6015(8) Å, β = 98.186(6)0, Z = 8, and R = 0.038. The macrocycle, 1,4,7,12,15,18‐hexathiacyclodocosane, crystallizes in the orthorhombic space group, Pbca, with a = 21.406(5) Å, b = 9.810(2) Å, c = 10.225(2) Å, Z = 4, and R = 0.020.
Convenient synthesis of 1‐alkoxy‐1,2‐dihydrophosphinine 1‐oxides by ring enlargement
Authors: Keglevich GyöRgy , Brlik JáNos , Janke Frank , Tőke László
Published: January 2005

The addition of dichlorocarbene to the double bond of 1‐alkoxy‐dihydrophosphole oxides and subsequent thermolysis of the adduct so obtained affords mixtures of the two double bond isomers of alkoxy‐dihydrophosphinine oxides, if the latter step is carried out in the presence of triethylamine. Experimental data support the involvement of a cationic intermediate during the opening of the cyclopropane ring. A simplified procedure for the preparation of the starting dihydrophospholes is also presented.
Synthesis and crystal structures of the triphenylstannyl esters of N‐phthaloyl‐glycine and ‐leucine
Authors: Ng Seik Weng , Das V. G. Kumar , Pelizzi Giancarlo , Vitali Francesca
Published: January 2005

Triphenyltin N‐phthaloylglycinate crystallizes from ethanol as a bridged, cyclic hexamer (rhombohedral R3 space group, a = 19.928(3) Å, α = 116.47(2)0; Z = 6) and triphenyltin N‐phthaloylleucinate as a monomeric molecule (orthorhombic Pbca space group, a = 18.032(6), b = 26.992(7), c = 11.705(4) Å; Z = 8).
arachno‐Diazapentaboranes
Authors: Küpper Stefan , Englert Ullrich , Paetzold Peter
Published: January 2005

The reaction of appropriate amounts of BH3 with diazadiboretidines (RBNtBu)2 (1a–e; R = Et, Pr, Bu, tBu, tBu(Me3Si)N) transforms them into cyclic diazapentaboranes either of the type [RB(H2)BRNtBuBHNtBu] (2a–c), of the type [HB(H2)BRNtBuBHNtBu] (3a–d), or of the type [HB(H2)BHNtBuBHNtBu] (4), or into an acyclic product RBHNtBuBHNtBuBHR (2e). The structure of 3c is characterized by a planar N2B3 ring skeleton with an unsymmetrical double‐hydrogen bridge.
Steric aspects of selectivity of organophosphorus extractants
Authors: Kabachnik M. I.
Published: January 2005

This paper is devoted to the steric aspects of the efficiency and selectivity of extractants in the process of extraction of metal cations from acidic aqueous solution into a nonpolar phase. The extraction of uranium, plutonium, americium, and europium by tertiary carbamoylmethyl phosphine oxides and polydiphenylphosphinylmethyl benzenes have been studied. The separation factors of uranium and plutonium from americium are measured. Tertiary carbamoylmethyl phosphine oxides and diphenylphosphinylmethyl benzenes of the ortho type are characterized by unusually high separation factors. The diphenylphosphinylmethyl derivatives of benzene of the meta type do not possess a high selectivity in the process of separation of uranium and plutonium from americium, but are more efficient in extraction of americium.
Investigations of a highly crowded phosphino‐substituted biphenyl: A precursor for a λ3, λ5‐diphosphaphenanthrene
Authors: Van Den Winkel Yvar , Van Der Laarse Jeroen , De Kanter Frans J. J. , Van Der Does Thomas , Bickelhaupt Friedrich , Smeets Wilberth J. J. , Spek Anthony L.
Published: January 2005

The synthesis of 2,2′‐bis(bis(dimethylamino)‐phosphino)‐3,3′5,5′‐tetra‐tert‐butylbiphennyl (5) is described. It was extensively studied by 1H, 13C, and 31P NMR spectroscopy. Furthermore, the X‐ray analysis of 5 is reported. Crystals of 5 are tetragonal, space group P¯421c, a = b = 24.770 (3) Å, c = 12.658 (4) Å, Z = 8. The surprising reaction of 5 with proton acids leading to the formation of various phosphorus containing five‐ and six‐membered ring compounds is discussed. On reaction of one of the six‐membered ring compounds (9) with magnesium in THF, a λ3, λ5‐diphosphaphenanthrene (19) was obtained.
A phosphoranide (10‐P‐4) anion coordinating to transition metals, as a Lewis base and a π‐acceptor
Authors: Chopra Suman K. , Martin J. C.
Published: January 2005

The reaction of 10‐P‐5 hydridophosphorane 6 with KH provides the 10‐P‐4 potassium phosphoranide anion 7a. Anion 7a reacts with CpFe(CO)2I and BrAu(PEt3) to replace the halide with the phosphoranide as a monodentate ligand forming 8 and 9. The X‐ray structure of 8 shows that the equatorial—Fe(CO)2Cp ligand of 8 makes the apical PO bonds (1.824 Å) longer than the PO bonds (1.80 Å) of the phosphoranide oxide anion 10. The PO bonds (1.75 Å) of 6, with an equatorial proton ligand, are still shorter. This provides evidence that the—Fe(CO)2Cp ligand is not only a sigma‐acceptor Lewis acid ligand, but also a pi‐donor that transfers electrons into the OPO three‐center bond's anti‐bonding orbital to increase its P—O bond lengths. It is a better pi‐donor than the O− pi‐donor of phosphoranide oxide 10.
Unusual formation of a λ 6P‐tetrafluorophosphate involving intramolecular donor–acceptor interaction; x‐ray crystal structure analysis and temperature‐dependent NMR‐spectra
Authors: Kaukorat Thomas , Jones Peter G. , Schmutzler Reinhard
Published: January 2005

The N,N,N′‐trimethylethylenediaminetetrafluorophosphate, 4, was formed in the unusual reaction of N,N,N′‐trimethyl‐N′‐trimethylsilylethylenediamine, 1, with the NP‐bonded tetrafluorophosphoranes, dimethylaminotetrafluorophosphorane, 2, or morpholinotetrafluorophosphorane, 3. There was no evidence for the cleavage of a PF bond in the tetrafluorophosphoranes (with formation of Me3SiF); instead, the SiN compounds, R2NSiMe3 (R2 = Me2 or O(CH2CH2)2) were formed. The 19F and 31P NMR spectra of 4 at room temperature indicated dynamic behavior. The X‐ray crystal structure analysis of 4 revealed the presence of a five‐membered ring, formally as a result of intramolecular donor–acceptor interaction (PN = 196.5 pm) between the nitrogen atom of the Me2N group and phosphorus.
The synthesis of P‐chiral optically pure phosphorothioates, phosphorotrithioates, phosphoroselenothioates, methanephosphonothioates, and methylphenylphosphinothioates
Authors: KrzyżZanowska BożZenna , Stec Wojciech J.
Published: January 2005

Enantiomers of representative alkyl esters of phosphorothioic (7), phosphorodithioic (6), phosphorotrithioic (11), phosphoroselenothioic (9), methanephosphonothioic (28), methanephosphonodithioic (25), and methylphenylphosphinothioic (31) acids were prepared from corresponding pure diastereoisomers of N‐[R(+)‐ or S(‐)‐α‐methylbenzyl] phosphamidochalcogenates (e.g. 2, 3, 12, 17, 23, 26, and 30) via PN → PX conversion, which has been proved to proceed with full retention of configuration at phosphorus.
Peculiarities of pπpπ conjugation in aminosubstituted phosphaalkenes
Authors: Chernega Alexander N. , Ruban Alexander V. , Romanenko Vladislav D. , Markovski Leonid N. , Korkin Anatoly A. , Antipin Mikhail Yu. , Struchkov Yuri T.
Published: January 2005

Effets of pπpπ conjugation in phosphaalkenes have been considered by taking into account the results of X‐ray structural studies and ab initio quantum‐chemical calculations. The structural consequences of the conjugation depend to a certain extent on the character of the substituent and the place of its attachment to the double PC bond. Depending on the location of the substituent, bond polarization may strengthen or weaken (compensate for) the conjugation effects. A high contribution of the s‐character of the lone electron pair of the P atom is an essential feature of the electron structure of a phosphaalkene.
Coupling of two phosphaalkynes via a carbonyl group in the addition across a rhrh double bond
Authors: Hitchcock Peter B. , Maah Mohd Jamil , Nixon John F.
Published: January 2005

Phosphaalkynes, RCP (R = But, Adamantyl), add across the RhRh double bond of [Rh2Cp(CO)2] to give either [Rh2Cp(μ‐CO)(COPCR)] or [Rh2Cp(CO){PCRC(O)CRP}] depending on the stoichiometry of the reaction (Cp* = η5‐C5Me5). The structures of these complexes have been elucidated by NMR spectroscopy and by a single crystal X‐ray study on [Rh2Cp(CO){PCAdC(O)CPAd}]. Small amounts of the 1,3‐diphosphacyclobutadiene complexes [RhCp*(P2C2R2)] and the trinuclear compound [Rh3Cp(CO)2] are also formed in these reactions. The reactions of RCP with [CoRhCp2*(CO)2] are also described.

A preliminary account of part of this work has appeared in J. Chem. Soc., Chem. Commun., 1987, 658.
Products derived from oxidations of 3,4‐dimethyl‐1‐phenylphosphole‐1‐oxide: A 3‐phenyl‐5,6‐dimethyl‐2,3‐oxaphosphabicyclo[2.2.2]octene‐3‐oxide derivative as a precursor of phenyl metaphosphonic anhydride
Authors: Quin Louis D. , Wu Xiao‐Ping
Published: January 2005

Oxidation of 3,4‐dimethyl‐1‐phenylphosphole with peracids or peroxides gives a relatively stable P‐oxide, which can be used in Diels‐Alder reactions to give derivatives with the 7‐phosphanorbornene framework. Oxygen insertion into a C–P bond of this framework occurs smoothly with m‐ chloroperbenzoic acid (MCPBA) providing derivatives of the 2,3‐oxaphosphabicyclo [2.2.2] octene ring system. The phosphole can be converted to this system in a one‐pot synthesis by reaction with excess MCPBA in the presence of N‐phenylmaleimide as dienophile. The phosphole oxide undergoes mono‐epoxidation with MCPBA. Thermal or photochemical fragmentation of the 2,3‐oxaphosphabicyclo [2.2.2] ocetene is a useful source of the 3‐coordinate species Ph–PO2, a meta‐anhydride of phenylphosphonic acid. This species was trapped successfully with a variety of alcohols.
The syntheses and structures of iron carbonyl adducts of tricoordinated hypervalent phosphorus compounds
Authors: Arduengo Anthony J. , Lattman Michael , Dixon David A. , Calabrese Joseph C.
Published: January 2005

The hypervalent phosphorus compound 3,7‐di‐t‐butyl‐5‐aza‐2,8‐dioxa‐1‐phosphabicyclo[3.3.0]octa‐2,4,6‐triene(ADPO), forms a monosubstituted adduct, ADPO·Fe(CO)4, by direct reaction of 10‐P‐3 ADPO with Fe2(CO)9 or Fe(CO)5, as well as by reaction of 1,1‐dichloro‐3,7‐di‐t‐butyl‐5‐aza‐2,8‐dioxa‐1‐phosphabicyclo[3.3.0]octa‐3, 6‐diene(ADPO·Cl2) with Na2[Fe(CO)4]. The X‐ray crystal structure of ADPO·Fe(CO)4 shows that ADPO is coordinated to the iron through the phosphorus. The phosphorus of the adduct has a tetrahedral 8‐P‐4 geometry in contrast to the planar T‐shaped geometry of uncomplexed 10‐P‐3 ADPO. Ultraviolet photolysis of ADPO·Fe(CO)4 yields the disubstituted species (ADPO)2·e(CO)3 wherein ADPO has dimerized via P–O bond cleavage to form a bidentate (ADPO)2 ligand containing a 10‐membered ring that bridges axial and equatorial positions at the trigonal bipyramidal iron center.
Reactions of a P‐chloro‐iminophosphane with main group nucleophiles: Syntheses and x‐ray crystal structure analyses of two 1,3‐diphosphatetraz‐3‐ene derivatives
Authors: Hein Joachim , Gärtner‐Winkhaus Christiane , Nieger Martin , Niecke Edgar
Published: January 2005

The reactions of chloro(2,4,6‐tri‐tert‐butylphenylimino)phosphane with lithium tris(trimethylsilyl)silanide and lithium diphenylketimide furnish products resulting from the incorporation of a second chloroiminophosphane molecule into the primary substitution product and subsequent nucleophilic displacement of the chlorine ligand. The final products have been characterized by X‐ray structure analyses, which revealed some remarkable features.
Reduction of elemental selenium by samarium diiodide: Selective synthesis of diorganyl selenides and diselenides
Authors: Sekiguchi Masahito , Tanaka Hiromichi , Takami Noriaki , Ogawa Akiya , Ryu Ilhyong , Sonoda Noboru
Published: January 2005

The reduction of elemental selenium by samarium diiodide led to selective formation of selenolate anion species (Se2− and Se22−), the alkylation of which provided dialkyl selenides and diselenides, respectively, in excellent yields.
1λ5,3λ5‐Diphospholium ions
Authors: Schmidpeter Alfred , Mayer Peter , Stocker Johanna , Roberts Kenneth A. , Stang Peter J.
Published: January 2005

One example each is given for the reaction of bromoacetylenes and ethynyl‐phenyliodonium tosylates with bis(diphenyl phosphino)methane. The yellow crystalline 1:1‐addition products are diphospholium salts. They readily and selectively hydrolyze to give 2‐phosphinoylethenyl phosphonium salts.
1,2,4‐Azadiphosphole
Authors: Ionkin A. S. , Ignat'Eva S. N. , Litvinov I. A. , Naumov V. A. , Arbuzov B. A.
Published: January 2005

tert‐Butylaminophosphaalkyne 4 is shown to dimerize in alkaline medium to 1‐tert‐butyl‐3‐tert‐butylamino‐1,2,4‐azadiphosphole 1—the first representative of 1,2,4‐azadiphospholes. The structure of 1 has been determined by IR and 31P NMR spectroscopy and by X‐ray crystallography. Compound 1 crystallizes in the triclinic space group P¯1 with a = 10.356(7), b = 11.817(5), c = 11.830(3) Å, α = 88.51(3), β = 78.61(4), γ = 77.05(4)°, V = 1383(1) Å3, Z = 4 (two independent molecules).
The synthesis and thermal property of sodium cyclo‐octaphosphate
Authors: Watanabe Makoto , Honda Tomohiko
Published: January 2005

Sodium cyclo‐octaphosphate heptahydrate, (NaPO3)8 · 7H2O, has been made by heating lead cyclo‐tetraphosphate at 340°C, dissolving the thermal product in a 3% aqueous solution of tetrasodium ethylene‐diaminetetraacetate, and then crystallizing it by addition of sodium chloride and acetone to the solution. When the cyclo‐octaphosphate was heated up to 400°C, it decomposed to produce phosphates with both shorter and longer chain lengths. A main product at 300° to 350°C was sodium cyclo‐triphosphate, and the thermal product melted at about 630°C.
Molecular and crystal structure of tert‐butylphosphaethyne
Authors: Chernega Alexander N. , Antipin Mikhail Yu. , Struchkov Yuri T. , Meidine Mohamed F. , Nixon John F.
Published: January 2005

The crystal and molecular structure of tert‐butylphosphaethyne, ButCP, liquid at room temperature, has been determined by X‐ray diffraction at 108 K. Main geometrical parameters are as follows: PC 1.542(2), C(sp)–C(sp3) 1.470(3) Å, PCC 179.3(2)°.
Carbapenem antibiotics: Displacement of C‐3 sulfur side chain by another thiol moiety, and quaternization of a weaker pyridine nitrogen over a stronger primary amine (preparation of BMY 40732 and BMY 40886)
Authors: Rao Vanga S. , Rémillard R. , Ménard Marcel
Published: January 2005

Displacement of sulfoxide moiety by a thiol group is shown to be useful in the preparation of 6‐aminoethyl carbapenem derivatives. Also described is a simple strategy to mask a stronger basic primary amine as a nonbasic, nonnucleophilic imine in order to preferentially alkylate (quaternize) a weaker nitrogen of a pyridine in the same molecule. A discussion on the conformational aspects of the β‐lactam‐opened products is also presented.
17O NMR spectroscopy: Proton–oxygen coupling in simple alcohols at natural abundance
Authors: Chandrasekaran Subramanian , Boykin David W.
Published: January 2005

17O NMR data are reported for 3‐pentanol (1), cyclopentanol (2), cyclohexanol (3), and cycloheptanol (4). The 17O NMR signals for 1–4 appeared as doublets, shown to arise from proton–oxygen coupling (1JOH = 76 ± 3 Hz) by proton decoupling experiments. The effect of concentration, temperature, and solvent was examined in detail for 2. Proton—oxygen coupling was observed at low concentrations, decreased at lower temperatures, and was sensitive to solvent.
1,2,3‐Selenadiazoles as precursors to cyclopentadienylcobalt dithiolenes and 1,4‐dithiins: molecular structures of bis(cycloocteno)‐1,4‐dithiin and bis(cycloocteno)‐1,4‐diselenin
Authors: Dorrity Michael R. J. , Lavery Ann , Malone John F. , Morley Christopher P. , Vaughan Richard R.
Published: January 2005

Cycloocteno‐1,2,3‐selenadiazole (1) and cyclopenta‐dienyldicarbonylcobalt (2) react in the presence of an excess of elemental sulfur to yield the dithiolene cyclopentadienyl(1,2‐cyclooctenedithiolato)cobalt (3). Available evidence indicates that this reaction involves the intermediacy of a cobalt–alkyne complex. Compound 3 is the first example of a cyclopentadienylcobalt dithiolene bearing aliphatic substituents. Analogous reactions performed using only catalytic quantities of 2 provide high‐yield syntheses of bis(cycloocteno)‐1,4‐dithiin (6) and bis(cycloocteno)‐1,4‐diselenin (7), whose structures have been determined by X‐ray diffraction.
Phosphorylated derivatives of 1‐morpholinocyclohexene and cyclohexanone
Authors: Tolmachev Andrew A. , Kostyuk Alexander N. , Kozlov Ernest S. , Chernega Alexander N. , Pinchuk Alexander M.
Published: January 2005

Phosphorylation of a relatively simple enamine with phosphorus (III) halides was first exemplified by the behavior of 1‐morpholinocyclohexene. Novel types of functionalized P(III) derivatives have now been obtained and studied. The hydrolysis of (2‐morpholino‐1‐cyclohexenyl) tetraethyldiamidophosphazidoarenes was found to be accompanied by the migration of the triazene group from the phosphorus atom to the carbon atom of the cyclohexene ring.
MNDO calculations on boron–nitrogen derivatives of nonbenzenoid aromatics: I. The two fully boron–nitrogen‐alternating isomers of “inorganic azulene”
Authors: McFarland Jennifer D. , Welk Natalie A. (Jackson) , Zoellner Robert W.
Published: January 2005

Modified neglect of diatomic overlap (MNDO) calculations have been used to investigate the ground state properties of the two fully boron‐nitrogen‐alternating isomers of “inorganic azulene”: 1,3,4,6,8‐pentaaza‐2,3a, 5,7, 8a‐pentaboraazulene (1, 1,3,4,6,8‐PAPBAZ) and 2,3a,5,7,8a‐pentaaza‐1,3,4,6,8‐pentaboraazulene (2, 2,3a,5,7,8a‐PAPBAZ). Both molecules optimize to planar structures, have exothermic heats of formation (−194.4 kcal/mol and −161.4 kcal/mol, respectively), and exhibit some bond delocalization. The relationship of these two PAPBAZ isomers to their organic parent molecule, azulene, is discussed.
Synthesis of carboranes containing nucleoside bases
Authors: Yamamoto Yoshinori , Seko Toshiya , Nakamura Hiroyuki , Nemoto Hisao
Published: January 2005

The carboranes containing uridine derivatives (9a,b,c), and purine base (8) were prepared by the reaction of decaborane with the corresponding acetylene precursors (3a, 3b, 2c and 5b, respectively).
Facile and convenient synthesis of B‐amino‐9‐borabicyclo[3.3.1]nonanes. Aminoboration of lsocyanates
Authors: Singaram Bakthan
Published: January 2005

The reaction of 9‐borabicyclo[3.3.1]nonane (9‐BBN) with aliphatic and aromatic primary and secondary amines in tetrahydrofuran (THF) at 65°C proceeds rapidly and quantitatively with evolution of hydrogen and the formation of the corresponding B‐amino‐9‐borabicyclo[3.3.1] nonane (B‐amino‐9‐BBN). Simple evaporation of THF from the reaction mixture gives the B‐amino‐9‐BBN derivatives in high yield and purity. These B‐amino‐9‐BBN derivatives are reactive towards alkyl and aryl isocyanates. Consequently, the aminoboration of various isocyanates has been studied using B‐phenylamino‐9‐BBN. Thus, two equivalents of isocyanates react with one equivalent of B‐phenylamino‐9‐BBN to afford, following the hydrolysis of the intermediate with ethanolamine, N, N'‐disubstituted‐N ‐(phenylamido)‐ureas in excellent yields. A plausible mechanism for this aminoboration reaction of isocyanates is also presented.
Hindered organoboron groups in organic synthesis. 17 [1]. Synthesis of 2,4,6‐triisopropylphenylborane (TripBH2)2, a useful alternative to thexylborane
Authors: Pelter Andrew , Smith Keith , Buss Dieter , Jin Zhao
Published: January 2005

2,4,6‐Triisopropylphenylborane (tripylborane, TripBH2) resembles thexylborane in having a single, bulky organic group attached to boron, but the group is aromatic rather than aliphatic. The compound has been synthesized by two alternative routes, one involving direct reduction of dimethoxytripylborane and the other involving redistribution between ditripylborane and borane. It is a solid which is considerably more stable than thexylborane.
Halogenolysis of Se‐methyl phosphinoselenoates
Authors: Krawiecka B.
Published: January 2005

The reaction of the title phosphinoselenolates with sulfuryl chloride and halogens was investigated stereochemically and spectroscopically (31P NMR at variable temperatures). Differences were observed in the reaction course when compared to the behavior of sulfur analogs towards the same reagents. The good donor character of the selenium atom and the leaving ability of the –Se+(R)X group explain well the results of the investigation.
Molecular and electronic structure of selenium and tellurium tetrahalides
Authors: Novak Igor
Published: January 2005

Molecular and electronic structures of MX4 (M = Se, Te: X = F, Cl) were studied by the ab initio method with extended basis sets. The study is aimed at supplementing very scarce experimental information about these molecules. The results indicate that all molecules favour distorted disphenoidal geometries (C2v point group) in preference to a C4v geometry. A possibly interesting phenomenon of energy stabilisation by having bonds of different polarities within the same molecule has been observed in SeCl4 and TeCl4.
Synthesis and characterization of functional cyclopentasilanes
Authors: Jenkner P. K. , Spielberger A. , Hengge E.
Published: January 2005

Cleavage of the exocyclic Si‐Si‐bond of phenyldimethysilylnonamethylcyclopentasilane3by sodium ethoxide followed by chlorination with acetyl chloride leads to the monofunctional chlorononamethylcyclopentasilane5. Subsequent hydration gives hydrononamethylcyclopentasilane6, which can be easily converted to the corresponding bromo and iodo derivatives7,8. Fluorononamethylcyclopentasilane can be prepared upon treatment of7with ZnF2. A different but convenient synthetic pathway to the halononamethylcyclopentasilanes has also been achieved employing the corresponding trifluoromethanesulfonic acid ester11. The halogen derivatives—as expected—show a strong influence on the physical properties of the compounds.

These functionalized cyclopentasilanes may serve as useful synthetic tools in building larger oligosilane ring systems.
Studies on organophosphorus compounds 56. New reaction of dialkyl phosphites with 2‐nitrostyrene derivatives—a facile route to N‐hydroxy‐3‐indole phosphonates and indol‐2‐one phosponates
Authors: Wang Guohong , Yuan Chengye
Published: January 2005

Reaction of a dialkyl phosphite with a 2‐nitrostyrene in the presence of triethylamine, trimethylsilyl chloride, and hexamethyldisilazane provides a one‐pot procedure for the synthesis of an N‐hydroxy‐indole‐3‐phosphonate and an indole‐2‐one‐3‐phosphonate besides the normal addition product, a 1‐aryl‐2‐ni‐troalkylphosphonate. Such new indole derivatives are difficult to prepare by conventional methods. The ratios of reactant to silylating agent and base were found to have significant influence on the product composition. The mechanism of formation of these het‐erocyclic products is discussed.
Synthesis and reactions of optically active phosphine‐boranes
Authors: Imamoto Tsuneo , Oshiki Toshiyuki , Onozawa Takashi , Matsuo Masatoshi , Hikosaka Takaaki , Yanagawa Masao
Published: January 2005

Synthesis and reactions of optically active phosphine‐boranes have been investigated. Optically active secondary phosphine‐boranes, (Sp)‐and (Rp)‐menthyloxyphenylphosphine‐boranes, and (S)‐methylphenylphosphine‐borane underwent palla‐dium(0)‐catalyzed electrophilic arylation with o‐, m‐, or p‐iodoanisole. The stereochemistry of this arylation was largely dependent on the solvent and the base used. The reaction in acetonitrile proceeded with almost complete retention of configuration at the chiral phosphorus, whereas inversion of configuration was observed in ethereal solvents or toluene. The phosphorus‐oxygen bond of (Rp)‐menthyloxy (methyl) phenylphosphine‐borane and (SP)‐menthy‐loxy(o‐methoxyphenyl)phenylphosphine‐boranewas reductively cleaved at −78°C by lithium naphtha‐lenide or Li/NH3 with virtually net retention of configuration at phosphorus, providing secondary or tertiary phosphine‐boranes in excellent yields. New synthetic routes to optically pure C2‐symmetric bisphosphine‐boranes possessing chirality at phosphorus have been developed on the basis of these stereochemical studies.
Reaction of phenyliodonium ylides of β‐dicarbonyl compounds with allylic sulfides and selenides
Authors: Yang Rui‐Yang , Dai Li‐Xin , Ma Ru‐Jian
Published: January 2005

An efficient and mild reaction for introducing an allylic moiety and an alkylthio‐ or alkylseleno‐group onto the α‐carbon of β‐dicarbonyl compounds in one step by tandem transylidation and [2,3]‐sigmatropic rearrangement is described.
Syntheses and characterization of pentacoordinate organo‐tin(IV) complexes
Authors: Wang Ji‐Tao , Zhang Yun‐Wen , Xu Yu‐Ming , Wang Zhi‐Wen
Published: January 2005

Ten novel pentacoordinate organo‐tin complexes were prepared and characterized. Single crystal structure determinations by X‐ray diffraction and also chemical investigations were made.
The reaction of dipolarophiles with arenealdoxime dehydrodimer
Authors: Wei Xudong , Zhang Zhuangyu , Li Jiaming , Hu Hongwen
Published: January 2005

The reactions of dipolarophiles with arenealdoxime dehydrodimers 1 have been studied. The reaction products depend upon the dipolarophile used. The reaction of 1 with styrene afford linear adducts. Active dipolarophiles, such as methyl acrylate and dimethyl acetylenedicarboxylate, lead to 1,3‐cycloaddition products. The possible mechanisms for both cases are discussed.
Crystal and molecular structure of 5,5‐dimethyl‐1,3‐dithian‐2‐ylcarboxylic acid. Is the axial conformer stabilized by hydrogen bonds?
Authors: Mikołajczyk Marian , Graczyk Piotr P. , Wieczorek Michał W. , Błaszczyk Jarosław
Published: January 2005

The crystal structure of the title compound (3) was determined by the X‐ray diffraction technique from diffractometer intensity measurements: C7H12O2S2, monoclinic space group P21/c, a = 12.644(1) Å, b = 6.102(1) Å, c = 12.920(2) Å, B = 110.78(1)°, 2193 reflections, and R = 0.043. The molecule of (3) adopts a chair conformation in which the carboxyl group occupies an axial position. The contacts between the carbonyl oxygen and axial hydrogens at C(4) and C(6) of 2.564 and 2.697 Å are smaller than the sum of van der Waals radii of this oxygen and hydrogen atoms, indicating a possibility of intramolecular CO· ·HC hydrogen bond formation. The acid 3 forms also dimeric structures via intermolecular hydrogen bonds with contact between hydroxyl hydrogen and carbonyl oxygen of 1.439 Å and OH· · ·O angle of 176.2°.
Insertion of CS2 into CuS bonds (II). Preparation and crystal structure of insertion product with CS2 [Cu6(S2CSC6H2Pri3‐2,4,6)4(SC6H2Pri3‐2,4,6)2] · 2CHCl3 · 4CH3OH
Authors: Tang Kaluo , Wu Dedong , Jin Xianglin , Tang Youqi
Published: January 2005

Complex [Cu(SC6H2Pri 3‐2,4,6)]8 (1) reacts with a small amount of CS2 to give red crystals [Cu6(S2CSC6H2Pri3‐2,4,6)4(SC6H2Pri3‐2,4,6)2] · 2CHCl3 · 4CH3OH (2), and CS2 is inserted into two‐thirds of the CuS bonds of complex (1). The unusual structure of complex (2) consists of six copper atoms linked through arenethiolate (RS−) and aryl trithiocarbonate (RSCS2−) ligands, exhibiting a number of interesting features. Crystal data: triclinic, space group P1, a = 14.298(4), b = 14.282(5), c = 17.745(7)Å, α = 109.92(3), β = 111.88(3), γ = 90.42(2)°, Z = 1, R = 7.83%, for 4118 observed reflections.
Occurrence of ligand coupling in the reaction of the 2‐thienyl sulfoxides with organometallic compounds
Authors: Oae Shigeru , Inubushi Yoichi , Yoshihara Masakuni
Published: January 2005

Treatment of 2‐pyridyl 2‐thienyl sulfoxide with 2‐thienyllithium was found to give both 2‐(2‐pyridyl)thiophene 2 and 2,5‐(di‐2‐pyridyl)thiophene 3. The reaction between 2‐thienyllithium and thionyl chloride was found to give 2,2′‐bithienyl 8, a coupling product, which is also formed by the reaction between di‐2‐thienyl sulfoxide 7 and 2‐thienyllithium.
Oxygen‐18 labeling of cyclic and acyclic sulfinate esters
Authors: Okuyama Tadashi , Senda Koji , Takano Hitomichi , Ando Noriyuki , Ohnishi Kazunori , Fueno Takayuki
Published: January 2005

Both cyclic and acyclic sulfinate esters were labeled with 18O at the sulfinyl oxygen by acid‐catalyzed isotope exchange with H218O or alkaline hydrolysis in H218O followed by re‐esterification. Long‐range 18O isotope effects on the 13C NMR chemical shifts were observed.
Facile reductive deamination of arylamines using a new arenesulfonyl nitrite
Authors: Shin Hyun Ho , Park Young Jun , Kim Yong Hae
Published: January 2005

Arenesulfonic acids were found to react with dinitrogen tetraoxide at −40°C in tetrahydrofuran to form arenesulfonyl nitrites which showed excellent diazotizing ability for the reductive deaminations of arylamines to arenes in the presence of anhydrous copper(II) halides as catalysts.