Trinuclear Metal Clusters with Three Different Metal Atoms from the Insertion of CpCo and Cp*Rh Groups into the S–S Bonds of [CpFeMn(CO)<Subscript>5</Subscript>(μ-S<Subscript>2</Subscript>)]<Subscript>2</Subscript><Superscript>†</Superscript>

Two cobalt containing products CpCoMn₂(CO)₆(μ₃-S)₂, 2 and Cp₂FeCoMn(CO)₃(μ₃-S)₂, 3 were obtained from the reaction of [CpFeMn(CO)₅(μ-S₂)]₂, 1 with CpCo(CO)₂ at room temperature. The two rhodium containing products: Cp*RhMn₂(CO)₆(μ₃-S)₂, 4 (11% yield) and CpFeCp*RhMn(CO)₃(μ₃-S)₂, 5 (9% yield), were obtained from the reaction of 1 with Cp*Rh(CO)₂. Compounds 3 and 5 were characterized structurally by single crystal X-ray diffraction methods. Compounds 3 and 5 both contain triangular clusters of three different types of metal atoms and have triply bridging sulfido ligands on each side of the cluster. A mechanism for their formation from 1 is proposed.^†Dedicated to F. A. Cotton on the occasion of his 75th birthday.     

Spontaneous formation of gel emulsions in organic solvents and commercial fuels induced by a novel class of amino acid derivatized surfactants

A novel class of amphiphiles, sodium N-(n-dodecyl-2-aminoethanoyl)-l-amino acidate, have been synthesized. These amphiphiles have been shown to form oil-in-water-type gel emulsions with a high internal-phase ratio in organic solvents as well as in commercial fuels simply by agitation. No heating and cooling cycle was required for the formation of gels. The amphiphiles also showed efficient phase-selective gelation in the presence of excess water. The minimum gelator concentrations for the amphiphiles in the solvents employed have been determined. The effects of the chain length of the hydrocarbon tail and the chirality of a representative amphiphile on its ability to promote gelation in a given organic solvent have been investigated. Also, the effect of acid and alkali on the gelation has been examined. The optical microscopic picture of the gel emulsion showed foamlike structures with oil compartments separated by the continuous aqueous phase. The mechanism of the formation of gel emulsions has been discussed.     

Measurement of local susceptibility at100Rh in some metallic hosts

The local susceptibilities (T) of isolated Rh impurities in Pb, Ru, Au, Pd, Pt andYb hosts have been measured as a function of temperature. The results show close to unity for Rh in Pb, Ru, Au andYb indicating nonmagnetic behaviour. In contrast, the magnetic response in exchange enhanced d band metal hosts, e.g. Pd andPt, shows Curie-Weiss-like local susceptibility andreflects a large quasi stable 4d magnetic moment on Rh.     

Synthesis and properties of oligomers of iron-manganese carbonyl complexes with bridging disulfido ligands

The reactions of activated CpFeMn(CO)₇1a and Cp*FeMn(CO)₇1b, Cp=C₅Me₅ with thiirane yielded the new dimeric mixed metal disulfido complexes: [CpFeMn(CO)₅(μ₃-S₂)]₂ (2) and [Cp*FeMn(CO)₅(μ₃-S₂)]₂ (3). Compounds 2 and 3 both contain two triply bridging disulfido ligands. When heated at 40 °C, compound 2 was transformed into a trimeric compound Cp₃Fe₃Mn₃(CO)₁₅(μ₃-S₂)(μ₄-S₂)₂, 4. Compound 4 contains three disulfido ligands, each of which has a different bridging coordination mode in the six atom metal cluster. There are three inequivalent CpFe(CO)₂ groupings linked to a central Mn₃(S₂)₃ core by the disulfido ligands. In solution, compound 4 exhibits a dynamical intramolecular exchange process that interconverts two of the three CpFe(CO)₂ groups on the NMR timescale.     

Optical effects of S-oxidation and M(n+) binding in meso-thienyl dipyrrin systems and of stepwise bromination of 4,4-difluoro-8-(2,5-dibromo-3-thienyl)-4-bora-3a,4a-diaza-s-indacene

We report 16 novel species and 8 molecular structures in studying how meso-thienyl-substituted dipyrrole oxidation, bromination, and metal ion binding impart optical changes, as monitored by UV-vis absorption/emission spectroscopy. Treatment of 4,4-difluoro-8-(3-benzothienyl)-4-bora-3a,4a-diaza-s-indacene (varphi(F) = 0.19) with m-CPBA gives selective S-dioxidation (varphi(F) = 0.006). Results of titrations of transition metal- and "scorpionate"-like dipyrrin species varied under room temperature treatment of m-CPBA. Ni-(thienyl-dipyrrin)(n) (n = 2) degraded significantly in the presence of m-CPBA, whereas related species (M = Cu, Fe, Co; n = 2, 3) were inert. meso-Thienyl group properties were revealed through the use of 3,4,4-triphenyl-8-(thienyl)-4-bora-3a,4a-diaza-s-indacene; Cu(2+) addition resulted in smooth absorption decreases which were modeled to support 1:1 substrate:M(2+) binding; for Hg(2+) 1:2 substrate:M(2+) binding was found. Treatment of 4,4-difluoro-8-(2,5-dibromo-3-thienyl)-4-bora-3a,4a-diaza-s-indacene with Br(2) gave red-shifted UV-vis absorption band features that grow with increasing dipyrrin bromination. Structures of the di- and tetra-substituted bromination products were obtained.     

Studies on liquid–liquid extraction of La(III) from acidic nitrate medium using TBP in petrofin

The present study aims at investigating the capability of tri-n-butyl phosphate (TBP) in petrofin as extracting agent for La(III) from acidic nitrate medium. The concentrations of TBP and sodium nitrate have positive influence while temperature shows a negative impact on the extraction. The values of standard enthalpy change and entropy change confirm the extraction process as exothermic with a decrease in randomness due to complexation. Regression analysis results fit well with the experimental data in the cases of TBP and nitrate concentration variation.     

Reactivity dynamics of a confined molecule in presence of an external magnetic field

Reactivity dynamics and stability of a confined hydrogen molecule in presence of an external magnetic field has been studied using quantum fluid density functional theory. Dynamic profiles of various reactivity parameters such as hardness, electrophilicity, magnetizability, phase volume, entropy, etc. have been studied within a confined environment. Responses in the reactivity parameters as well as the associated electronic structure principles validate the stability of the confined H₂ molecule in ground and excited states in presence of an external magnetic field. Confinement to the system has been imposed by the Dirichlet type boundary condition. Confinement and excitation act in opposite directions. Ground state type dynamics is obtained on simultaneous electronic excitation and confinement. © 2014 Wiley Periodicals, Inc.     

Photocatalytic Synthesis of β-Keto Primary Chlorides by Selective Chlorocarbonylation of Olefins

Functionalized primary alkyl chlorides are precursors to a plethora of scaffolds but their access from chemical feedstocks remains challenging. Herein, we report a concise dual Ni/photoredox catalytic protocol for regioselective chlorocarbonylation of unactivated alkenes that enables rapid access to β-keto primary chlorides. The catalytic process features an extensive substrate scope, scalability and functional group tolerance. The Ni/photocatalytic Cl⋅ generation and subsequent cross-coupling is implicated for the process based on the control experiments and DFT study. The synthetic utility of the protocol has been further corroborated through functionalization of complex substrates and modifications of the product.     

Effect of Processability on the Thermal Stability of the Blends Based on Polyurethane. Part II

Thermal stability of the blend of polyurethane with three other elastomers, having the reactive functional group, has been studied. Three different blending techniques have been employed to study the effect of processability on the thermal stability of the blend. IR spectral analysis revealed that interchain crosslinking takes place between the two elastomer phases. Thermal stability of the blend increased when preblending and preheating preblending techniques were applied, probably due to the formation of the interchain crosslink between the elastomer phases. This revised version was published online in August 2006 with corrections to the Cover Date.     

Adsorbed States of Hydrogen on Platinum: A New Perspective

The interaction of hydrogen with platinum is enormously important in many areas of catalysis. The most significant of these are in polymer electrolyte membrane fuel cells (PEMFC), in which carbon-supported platinum is used to dissociate hydrogen gas at the anode. The nature of adsorbed hydrogen on platinum has been studied for many years on single-crystal surfaces, on high-surface area-platinum metal (Raney platinum and platinum black), and on supported catalysts. Many forms of vibrational spectroscopy have played a key role in these studies, however, there is still no clear consensus as to the assignment of the spectra. In this work, ab initio molecular dynamics (AIMD) and lattice dynamics were used to study a 1.1 nm nanoparticle, Pt₄₄H₈₀. The results were compared to new inelastic neutron scattering spectra of hydrogen on platinum black and of a carbon-supported platinum fuel cell catalyst and an assignment scheme that rationalises all previous data is proposed.