The electronic states of biacetyl

The ordering of the lower electronic states of biacetyl is discussed and the consequences for the mechanism of the radiationless S → T transitions are considered in detail.     

Palladium catalysed copolymerisation of ethene with alkylacrylates: polar comonomer built into the linear polymer chain

Copolymerisation of ethene and alkylacrylates is catalysed by palladium modified with di(2-methoxyphenyl)phosphinobenzene-2-sulfonic acid (DOPPBS); a linear polymer is produced in which acrylate units are incorporated into the polyethylene backbone.     

Optimizing a phase gate using quantum interference

A controlled interference is proposed to reduce, by two orders of magnitude, the decoherence of a quantum gate for which the gate fidelity is limited by coupling to states other than the /0> and /1> qubit states. This phenomenon is demonstrated in an ultracold neutral atom implementation of a phase gate using qubits based on motional states in individual wells of an optical lattice.     

Spontaneous dissociation of long-range Feshbach molecules

We study the spontaneous dissociation of diatomic molecules produced in cold atomic gases via magnetically tunable Feshbach resonances. We provide a universal formula for the lifetime of these molecules that relates their decay to the scattering length and the loss rate constant for inelastic spin relaxation. Our universal treatment as well as our exact coupled channels calculations for 85Rb dimers predict a suppression of the decay over several orders of magnitude when the scattering length is increased. Our predictions are in good agreement with recent measurements of the lifetime of 85Rb(2).     

A torsional creep apparatus

Summary This paper describes a torsional creep apparatus for the determination of the creep compliance in shear as a function of time. The instrument is suitable for the measurement of compliances below 5·10^–8 m²/N, in the time range between 1 and 10⁵ seconds. Within five minutes and with an accuracy of 1 C, the temperature of the specimen can be adjusted to any value between –175 and –200 C. From the torsional creep measurements can be calculated the dynamic shear modulus and the corresponding damping. The lowest damping, determined in this way, is several times 10^–3.

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Zusammenfassung Ein Apparat zur Messung des Torsions-Kriechverhaltens wird beschrieben. Das Instrument ist zur Bestimmung von Nachgiebigkeiten kleiner als 5·10^–5 m²/N im Zeitbereich zwischen 1 und 10⁵ Sekunden geeignet. Die Temperatur der Probe läßt sich innerhalb 5 Minuten und mit einer Genauigkeit von 1 C auf jeden Wert zwischen –175 und –200 C einstellen. Aus der gemessenen Kriechfunktion können der dynamische Schubmodul und die dynamische Dämpfung berechnet werden. Eine untere Grenze für die Dämpfung, die man auf diese Weise noch bestimmen kann, ist einige Male 10^–3.

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The work was partly sponsored by the Office of Naval Research, Washington, D. C., under contract number N 62558-3884.     

Carbonylation of nitrobenzene in methanol with palladium bidentate phosphane complexes: an unexpectedly complex network of catalytic reactions, centred around a Pd-imido intermediate

The reactivity of palladium complexes of bidentate diaryl phosphane ligands (P₂) was studied in the reaction of nitrobenzene with CO in methanol. Careful analysis of the reaction mixtures revealed that, besides the frequently reported reduction products of nitrobenzene [methyl phenyl carbamate (MPC), N,N′‐diphenylurea (DPU), aniline, azobenzene (Azo) and azoxybenzene (Azoxy)], large quantities of oxidation products of methanol were co‐produced (dimethyl carbonate (DMC), dimethyl oxalate (DMO), methyl formate (MF), H₂O, and CO). From these observations, it is concluded that several catalytic processes operate simultaneously, and are coupled via common catalytic intermediates. Starting from a P₂Pd⁰ compound formed in situ, oxidation to a palladium imido compound P₂Pd^II?NPh, can be achieved by de‐oxygenation of nitrobenzene 1) with two molecules of CO, 2) with two molecules of CO and the acidic protons of two methanol molecules, or 3) with all four hydrogen atoms of one methanol molecule. Reduction of P₂Pd^II?NPh to P₂Pd⁰ makes the overall process catalytic, while at the same time forming Azo(xy), MPC, DPU and aniline. It is proposed that the Pd–imido species is the central key intermediate that can link together all reduction products of nitrobenzene and all oxidation products of methanol in one unified mechanistic scheme. The relative occurrence of the various catalytic processes is shown to be dependent on the characteristics of the catalysts, as imposed by the ligand structure.     

Far-infrared investigation of the phase transition at 217 K in layer-structured TiCl3

Far-infrared measurements reveal a distortion in layer-structured TiCl₃ below 217 K. This is explained by the formation of pairs of covalently bonded Ti³⁺ ions below this temperature. The electronic contribution to the entropy increase above 217 K is attributed to the degree of freedom of the spin of the d electron localized on the Ti³⁺ ion.     

Selective O‐allylation of bisphenol A: toward a chloride‐free route for epoxy resins

The O‐allylation of bisphenol A (BPA) has been performed with the most selective catalysts for O‐allylation of phenols reported previously. Both the cyclopentadienyl–ruthenium catalysts and the palladium–diphosphine catalysts are capable of selectively performing single and double O‐allylation of BPA. An intriguing solvent effect is observed; the choice of the solvent is of key importance for both conversion and selectivity. The use of an excess of diallyl ether as allylating agent results in relatively high yields of the bisallyl ether of bisphenol A, while maintaining the high selectivity for O‐allylation. Copyright © 2010 John Wiley & Sons, Ltd.     

Scope, mechanism and diene inhibition of isomerization of allylic alcohols to saturated ketones catalyzed by ruthenium(II)-cyclopentadienyl complexes

The isomerization of 3-buten-2-ol to butanone catalyzed by Ru(II)Cp-complexes (Cp = η⁵-cyclopentadienyl) with phosphine and amine ligands is described. The reaction catalyzed by [RuCp(MeCN)₃](PF₆) and two equivalents of triphenylphospine is first order in substrate with a k_ini of 0.43 h⁻¹ and an initial TOF of 13,000 h⁻¹. The catalyst precursor complex [RuClCp(dppb)] (dppb = bis(diphenylphosphino)butane) has been characterized by X-ray diffraction. This compound features a seven-membered ring incorporating the ruthenium centre and the dppb ligand.Combination of two equivalents of primary, secondary or tertiary amines and [RuCp(MeCN)₃](PF₆) results in active catalyst precursors. Within each group, increasing the bulk of the ligand gives lower isomerization rates. The combined effects of optimal pK_a, nucleophilicity and steric bulk make RuCp-complexes with secondary amines the most active precursors. With di-n-butylamine, 745 turnovers can be reached after 1 h. ³¹P NMR spectra indicate that the resting state in the catalytic cycle is a complex in which 3-buten-2-ol is η²-coordinated through the alkene moiety. This implies that coordination of the oxygen moiety and concomitant β-hydrogen abstraction is the rate-limiting step. A counterintuitive result is that allylic alcohols bind stronger to RuCp complexes with phosphine ligands than dienes. Inhibition of the catalyst appears to be a result of interaction of the diene with a ruthenium-allyl alcohol complex, which is sufficiently strong to prevent coordination of the oxygen moiety of the allylic alcohol. This hinders orientation of the allylic alcohol substrate in a suitable way to undergo β-hydrogen abstraction, thereby blocking isomerization catalysis.     

Detection and reactivity of Pd((C8H14)PCH2 CH2 P(C8H14))(CHPhCH2Ph)(H) as determined by parahydrogen-enhanced NMR spectroscopy

Pd(bcope)(OTf)2 (where bcope is (C8H14)PCH2CH2P(C8H14)) is shown to react with an alkyne in the presence of parahydrogen to form alkyl hydrides, such as Pd(bcope)(CHPhCH2Ph)(H), that are detectable by NMR spectroscopy because the proton resonances of the alkyl arm appear with strongly enhanced signal strengths.