Interaction of Triosmium Complexes with Hydrogen Chloride: A Model for Fine-Tuning Regioselective Protonation in Metal Clusters

The reaction of Os₃(CO)₁₀(CNR)(NCMe) (1) with HCl was studied and this system was found to be a good model for observing the fine-tuning of site-selective protonation in metal complexes. Three products including the protonated species [(-H)Os₃(CO)₁₀(CNR)(NCMe)]⁺Cl^– (2), the bridging aminocarbyne complex (µ-Cl)Os₃(CO)₁₀(µ₂-C = NHR) (3), and the hydrido derivative (-H)Os₃Cl(CO)₁₀(CNR) (4) were obtained for the reaction. The site of protonation, either on the Os center or on the nitrogen atom of coordinated isocyanide, was tuned in a sensitive manner by the nature of the coordinated isocyanides, the polarity of the solvents, and the strengths of the acids, leading to different product distributions. The more electron withdrawing isocyanides (CNCH₂Ph, CNPh) favor the formation of the aminocarbyne complex 3. In a nonpolar solvent like cyclohexane the reaction afforded 3 as the main product. Furthermore, complex 2 was converted to (-H)Os₃(CO)₁₀(₂-CONHR) (5) upon hydrolysis, in which the coordinated isocyanide was transformed to a carboxamido group. This was verified by obtaining the deuterated species (-H)Os₃(CO)₁₀(₂-CONDPr) when [(-H)Os₃(CO)₁₀(CNPr)(NCMe)]⁺Cl^– (2a) was treated with D₂O in THF. The molecular structures of (µ₂-Cl)Os₃(CO)₁₀(µ₂-C = NHCH₂Ph) (3b) and (-H)Os₃Cl(CO)₁₀(CNPr) (4a) were determined by X-ray diffraction analyses. Complex 3b contains both bridging chloride and bridging aminocarbyne groups, whereas 4a contains a terminal chloride, a terminal isocyanide and a bridging hydride.     

Nonsteady-state oxidation of propylene on supported silver catalysts

Nonsteady-state epoxidation of propylene on silver has been studied to establish the reason for the low catalyst activity and selectivity that appear to be due to side reactions of the formation of hydrogen-deficient deposits.

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Degradation of passive layers of iron studied by conversion electron Mössbauer spectroscopy

Integral electron Mössbauer spectroscopy (ICEMS) and additionally some electrochemical methods were used to characterize the passivation process of iron (low carbon steel) in sulfate, sulfate+sulfite (a possible model solution of acid rain) solutions and in phospate buffer. The phase compositions and thicknesses of the passive layers formed due to the electrochemical polarizations were analyzed in dependence on the duration of the anodic passivations and on the pH of the used electrolytes. The passive layer, as determined from the Mössbauer spectra, consists mainly of -FeOOH, however in sulfite containing sulfate aqueous solution at pH 3.5 Fe₃C and despite ex-situ circumstances FeSO₄·H₂O was detected after the shortest polarization time. The film thickness, which was found to grow nearly linearly with polarization time in pure sulfate solution and in phospate buffer, reached a maximum of 60–160 nm (depending on pH) in sulfate+sulfite solution after a passivation time of about 4 hours. It has been proved, that HSO₃ ^–-ion, which is contained by acid rain, initiate pit formation under acid conditions and so enforces the corrosion of iron. The experimental results furthermore suggest, that not the whole oxidic layer is responsible for the passivity but only a very thin intermediate layer formed between an inner oxide layer of a cubic structure and the rhombic oxide (-FeOOH) cover.     

Some converses of the strong separation theorem

A convex subset of a real locally convex space is said to have the separation property if it can be separated from every closed convex subset of , which is disjoint from , by a closed hyperplane. The strong separation theorem says that if is weakly compact, then it has the separation property. In this paper, we present two versions of the converse and discuss an application of them. For example, we prove that a normed space is reflexive if and only if its closed unit ball has the separation property. Results in this paper can be considered as supplements of the famous theorem of James.

     

Synthesis, characterization, and structures of oxovanadium(V) complexes of Schiff bases of beta-amino alcohols as tunable catalysts for the asymmetric oxidation of organic sulfides and asymmetric alkynylation of aldehydes

Oxovanadium(V) complexes and with general formula VO(L3*)(OR5) were prepared in quantitative yields in alcohol (R5OH) from reactions of VO(O-i-Pr)3 and tridentate Schiff bases of beta-amino alcohols having one or two stereogenic centers, (HO)C*(R1)(R2)C*H(R3)N[double bond, length as m-dash]CH(2-OH-3,5-R4(2)-C6H2) (H2L3*). The alkoxy OR5 ligand exchanges readily with the alcoholic molecule in the solvent. Crystal structures of and were determined to be five-coordinate square pyramidal monomers. However, 1H NMR spectra of the complexes reveal two sets of signals, indicating the presence of two isomers in solution. The two isomers are suggested to be the endo/exo pair or the monomer/dimer pair. Asymmetric oxidations of methyl phenyl sulfide catalyzed by catalyst precursors were demonstrated to afford the chiral sulfoxide in yields and ee values similar to those obtained from the in situ-formed catalytic systems of VO(acac)2 and corresponding Schiff base ligands. Complexes and are also good catalysts for asymmetric alkynyl additions to aldehydes. Structural differences between the oxovanadium complexes, for inducing high stereoselectivities in the asymmetric oxidation of organic sulfides and the asymmetric alkynyl addition to aldehydes, are rationalized.     

-isomorphisms, Jordan isomorphisms, and numerical range preserving maps

Let or , where is the algebra of a bounded linear operator acting on the Hilbert space , and is the set of self-adjoint operators in . Denote the numerical range of by It is shown that a surjective map satisfies

if and only if there is a unitary operator such that has the form

where is the transpose of with respect to a fixed orthonormal basis. In other words, the map or is a -isomorphism on and a Jordan isomorphism on . Moreover, if has finite dimension, then the surjective assumption on can be removed.

     

AlAr3(THF): highly efficient reagents for cross-couplings with aryl bromides and chlorides catalyzed by the economic palladium complex of PCy3

Novel and highly efficient cross couplings of aryl bromides and chlorides with AlAr3(THF) (Ar = Ph, 2,4,6-Me3C6H2, 2-naphthyl or 4-Me3SiC6H4) catalyzed by the economic palladium catalyst of PCy3 are reported without the use of a base and under mild reaction conditions at room temperature or temperatures < or = 60 degrees C even for couplings of bulky aryl halides and the Al(2,4,6-Me3C6H2)3(THF) reagent.     

Sulfone–Metal Exchange and Alkylation of Sulfonylnitriles

The first general sulfone–metal exchange is described. Treating substituted 2-pyridylsulfonylacetonitriles with either BuLi or Bu₃MgLi generates metalated nitriles that efficiently intercept a variety of electrophiles to afford quaternary nitriles. The 2-pyridylsulfone is critical for the sulfone–metal exchange because chelation anchors the organometallic proximal to the electrophilic, tetrasubstituted sulfone to override complex-induced deprotonation. Alkylating commercial 2-pyridinesulfonylacetonitrile with mild bases, either K₂CO₃ or DBU, and subsequent sulfone–metal exchange and alkylation rapidly assembles quaternary nitriles by three alkylations, only one of which requires an organometallic reagent.