Synthesis, Molecular Structure, and 1H NMR Analysis of Bis(tetraphenylcyclopentadienyl)ruthenium(II)

Reaction of [Ru(p-cymene)Cl2]2 with K(η5-C5HPh4) in refluxing diglyme yields (η5-C5Ph4)2Ru in ca 50% yield. The complex was not susceptible to oxidation or reduction. (C5HPH4)2Ru crystallizes in the triclinic P1 space group with a = 8.549(4), b = 10.793(4), c = 12.842(5) Å, α = 65.98(3), β = 73.10(3), γ = 83.49(3)° and Z = 1. The least-squares data refined to R(F) = 3.53% and R(wF = 3.82% for the 3952 independent observed reflections with Fo ≥ 5σ(Fo). The metal-centroid distance is 1.832(2) Å and all other bond lengths and angles are similar to other octaphenylmetallocenes. 1H NMR analysis employing 2D J-resolved, COSY and low temperature techniques allowed assignment of all protons in the molecule. The motional processes of the phenyl groups are discussed

Manageable creativity

This article notes a perception in mainstream management theory and practice that creativity has shifted from being disruptive or destructive to 'manageable'. This concept of manageable creativity in business is reflected in a similar rhetoric in cultural policy, especially towards the creative industries. The article argues that the idea of 'manageable creativity' can be traced back to a 'heroic' and a 'structural' model of creativity. It is argued that the 'heroic' model of creativity is being subsumed within a 'structural' model which emphasises the systems and infrastructure around individual creativity rather than focusing on raw talent and pure content. Yet this structured approach carries problems of its own, in particular a tendency to overlook the unpredictability of creative processes, people and products. Ironically, it may be that some confusion in our policies towards creativity is inevitable, reflecting the paradoxes and transitions which characterise the creative process

Eigenvector localization as a tool to study small communities in online social networks

We present and discuss a mathematical procedure for identification of small "communities" or segments within large bipartite networks. The procedure is based on spectral analysis of the matrix encoding network structure. The principal tool here is localization of eigenvectors of the matrix, by means of which the relevant network segments become visible. We exemplified our approach by analyzing the data related to product reviewing on Amazon.com. We found several segments, a kind of hybrid communities of densely interlinked reviewers and products, which we were able to meaningfully interpret in terms of the type and thematic categorization of reviewed items. The method provides a complementary approach to other ways of community detection, typically aiming at identification of large network modules

Synthesis, Characterization, and Crystal Structure of the (η5-C5Ph5)Cr(CO)3 Radical

The reaction between Cr(CO)6 and Na(C5Ph5 ) in refluxing diglyme yields [Na(diglyme)3/2][(C5Ph5)Cr(CO)3], 1. Metathesis of 1 with [Ph3P=N=PPh3 ]Cl in CH2Cl2 yields [Ph3P=N=PPh3][(C5Ph5)Cr(CO)3], 2. Oxidation of 1 by AgBF4 in cold THF under an argon atmosphere produces (C5Ph5)Cr(CO)3, 3. Complexes 2 and 3 form a redox pair connected by a quasireversible one-electron process, E0 = -0.69 V vs ferrocene in CH2Cl2, E0 = -0.50 V in CH3CN, ks = 0.12 cm/s. ESR spectra of (C5Ph5)Cr(CO)3 in toluene at 90 K gave a rhombic g-tensor with components 2.1366, 2.0224, and 1.9953, consistent with the expected low-spin d5 electronic configuration. The largest g-tensor component was significantly temperature dependent, suggesting an equilibrium between conformations with 2A´ and 2A˝ ground states. Crystal structures of [Ph3P=N=PPh3][(C5Ph5)Cr(CO)3] and (C5Ph5)Cr(CO)3 were obtained

Collective emotions online and their influence on community life

E-communities, social groups interacting online, have recently become an object of interdisciplinary research. As with face-to-face meetings, Internet exchanges may not only include factual information but also emotional information - how participants feel about the subject discussed or other group members. Emotions are known to be important in affecting interaction partners in offline communication in many ways. Could emotions in Internet exchanges affect others and systematically influence quantitative and qualitative aspects of the trajectory of e-communities? The development of automatic sentiment analysis has made large scale emotion detection and analysis possible using text messages collected from the web. It is not clear if emotions in e-communities primarily derive from individual group members' personalities or if they result from intra-group interactions, and whether they influence group activities. We show the collective character of affective phenomena on a large scale as observed in 4 million posts downloaded from Blogs, Digg and BBC forums. To test whether the emotions of a community member may influence the emotions of others, posts were grouped into clusters of messages with similar emotional valences. The frequency of long clusters was much higher than it would be if emotions occurred at random. Distributions for cluster lengths can be explained by preferential processes because conditional probabilities for consecutive messages grow as a power law with cluster length. For BBC forum threads, average discussion lengths were higher for larger values of absolute average emotional valence in the first ten comments and the average amount of emotion in messages fell during discussions. Our results prove that collective emotional states can be created and modulated via Internet communication and that emotional expressiveness is the fuel that sustains some e-communities.Comment: 23 pages including Supporting Information, accepted to PLoS ON

Observation of a Distribution of Internal Transverse Magnetic Fields in a Mn12-Based Single Molecule Magnet

A distribution of internal transverse magnetic fields has been observed in single molecule magnet (SMM) Mn12-BrAc in the pure magnetic quantum tunneling (MQT) regime. Magnetic relaxation experiments at 0.4 K are used to produce a hole in the distribution of transverse fields whose angle and depth depend on the orientation and amplitude of an applied transverse ``digging field.'' The presence of such transverse magnetic fields can explain the main features of resonant MQT in this material, including the tunneling rates, the form of the relaxation and the absence of tunneling selection rules. We propose a model in which the transverse fields originate from a distribution of tilts of the molecular magnetic easy axes.Comment: 4 page

Halogen Oxidation Reactions of (C5Ph5)Cr(CO)3 and Lewis Base Addition To [(C5Ph5)Cr(μ-X)X]2: Electrochemical, Magnetic, and Raman Spectroscopic Characterization of [(C5Ph5)CrX2]2 and (C5Ph5)CrX2(THF) (X = Cl, Br, I). X-ray Crystal Structure of [(C5Ph5)Cr(μ-Cl)Cl]2

The 17-electron complex (C5Ph5)Cr(CO)3 reacts with halogens (C6H5I•Cl2, Br2, and I2) in C6H6 to yield the dimeric oxidation products [(C5Ph5)Cr(m-X)X]2 as thermally stable solids. Reactions with other chlorinating agents similarly yield [(C5Ph5)CrCl2]2. An X-ray crystal structure of [(C5Ph5)Cr(m-Cl)Cl]2 was obtained. The magnetic properties of the Cl2 bridged dimer have been determined and modeled using the usual isotropic hamiltonian which yields J/k = –30 K. Low-temperature (77 K) Raman spectra of solid [(C5Ph5)CrX2]2 (X = Cl, I) allow assignments to be made for the metal-ring and metal halogen stretching modes in the low frequency region (\u3c 600 cm-1). Tetrahydrofuran (THF) cleaves these dimers to yield complexes of the form (C5Ph5)CrX2(THF)

Role of radiography, MRI and FDG-PET/CT in diagnosing, staging and therapeutical evaluation of patients with multiple myeloma

Multiple myeloma is a malignant B-cell neoplasm that involves the skeleton in approximately 80% of the patients. With an average age of 60 years and a 5-years survival of nearly 45% Brenner et al. (Blood 111:2516–2520, 35) the onset is to be classified as occurring still early in life while the disease can be very aggressive and debilitating. In the last decades, several new imaging techniques were introduced. The aim of this review is to compare the different techniques such as radiographic survey, multidetector computed tomography (MDCT), whole-body magnetic resonance imaging (WB-MRI), fluorodeoxyglucose positron emission tomography- (FDG-PET) with or without computed tomography (CT), and 99mTc-methoxyisobutylisonitrile (99mTc-MIBI) scintigraphy. We conclude that both FDG-PET in combination with low-dose CT and whole-body MRI are more sensitive than skeleton X-ray in screening and diagnosing multiple myeloma. WB-MRI allows assessment of bone marrow involvement but cannot detect bone destruction, which might result in overstaging. Moreover, WB-MRI is less suitable in assessing response to therapy than FDG-PET. The combination of PET with low-dose CT can replace the golden standard, conventional skeletal survey. In the clinical practise, this will result in upstaging, due to the higher sensitivity