Fundamental metal carbonyl equilibria: a quantitative infrared spectroscopic study of the equilibrium between dicobalt octacarbonyl and tetracobalt dodecacarbonyl under carbon monoxide pressure in hexane solution.

The equilibrium between Co₂(CO)₈ and Co₄(CO)₁₂ has been investigated in hexane solution in the temperature range 105–145°C under carbon monoxide pressure (6–14 bar). the data obtained by infrared analytical monitoring of the system in a high-pressure cell alow a reasonably precise extension of the calculated equilibrium concentration between —20 and 300°C. The thermo- dynamic parameters obtained for this system are: ΔH⁰ 29.5 ± 0.5 kcal mol^-1, ΔS⁰ 135 ± 3 cal mol^-1 K^-1. The stability regions of Co₂(CO)₈ and Co₄(CO)₁₂ in terms of p(CO) and temperature are discussed.     

Kinetics and mechanism of the reaction of tetracobalt dodecacarbonyl with carbon monoxide under pressure

The kinetics of the reaction of tetracobalt dodecacarbonyl with carbon monoxide to form dicobalt octacarbonyl in n-hexane have been investigated over a wide range of temperature and CO pressure. The reaction is first order in [Co₄(CO)₁₂]; the order in [CO] changes between one (at low pressures and high temperatures) and two (at high pressures and low temperatures).Activation parameters have been estimated and a mechanism involving initial reversible breaking of one CoCo bond, followed by irreversible breaking of a second, is proposed. The first step involves concerted addition of CO while the second can proceed with or without such addition.     

Synthesis of D-Glucose-based Azacrown Ethers with Phosphinoxidoalkyl Side Chains and Their Application to an Enantioselective Reaction

Five chiral -D-glucose-based monoaza-15-crown-5 ethers with phosphinoxidoalkyl side chains of one to five carbon atoms (5a–e)have been synthesised. The cation binding ability of the new lariat ethers was evaluated bythe picrate extraction method. The substituents at the nitrogen atom were not a major influenceon the cation extraction ability of the azacrown ether; the compounds showed, however, a significant asymmetric induction as phase transfer catalysts in the Michael addition of2-nitropropane to chalcone (95% ee).     

Synthesis of alkyl α- and β-<Emphasis Type="SmallCaps">d</Emphasis>-glucopyranoside-based chiral crown ethers and their application as enantioselective phase-transfer catalysts

Chiral monoaza-15-crown-5-type lariat ethers annelated to alkyl 4,6-O-benzylidene-α- and β-d-glucopyranosides have been synthesized. These macrocycles generated significant asymmetric induction as phase-transfer catalysts in a few two-phase reactions. The catalytic effect of the lariat ethers with methoxy, ethoxy, and i-propoxy substituents on C-1 of the sugar unit in both α and β positions was compared. In liquid–liquid two-phase reactions, the nature and position of the substituents did not have much effect. The α-anomers were somewhat more efficient in terms of enantioselectivity than the β forms. In asymmetric Darzens condensations, in the epoxidation of trans-chalcone, in the Michael addition of β-nitrostyrene and diethyl acetamidomalonate, and in the reaction of 2-benzylidene-1,3-indandione with diethyl bromomalonate, maximum enantioselectivities of 73, 94, 78, and 72%, respectively, were obtained in presence of glucopyranoside-based lariat ethers as catalysts.     

“Comment” on the Reply to the Paper “On the Elber–Karplus Reaction Path-Following Method and Related Procedures”

The flaws in the Reply [1] to our paper [2] have been pointed out. Elber and Karplus (EK) have not disproved our irrefutable global statement that the energy average cannot be minimized which rebuts the theoretical background of EK-type calculations. Another statement of ours has shown that even a curve for which the average energy is locally minimal for all directional perturbations in the sense of classical variational calculus cannot be identical with the reaction path (RP) defined as a steepest descent path (SDP). EK found an error in the early preprint of our theoretical paper [3] and because of this error they qualified our correct variational statement as false for all the SDPs consisting of a straight line each. Mixing global and variational arguments, EK refuted our criticism in a logically incorrect manner. In this Comment we prove that both of our earlier statements invariably remain in force and the criticism included in those has been as well-established and solid as was before.     

The photochemical reaction cycle of retinal reconstituted bacteriorhodopsin

The function of three types of bacteriorhodopsins was compared: the wild-type, the bleached and retinal reconstituted and retinal deficient bacteriorhodopsin after retinal addition. The apparent pK(a) of the proton acceptor group for the bleached BR and retinal deficient BR shifted toward higher pH values compared to the wild-type BR. Fitting the photocycle model to the absorption kinetic signals for all three proteins showed the existence of the same intermediates, but the time-dependent concentration of the intermediates was different. Although measurements were made at pH 7, the absorption kinetics and photoelectric signals in both retinal reconstituted samples acted as wild-type bacteriorhodopsin at significantly higher pH. Below pH 3 the retinal deficient and reconstituted sample bleached. These results suggested that the added retinal was not able to rebind in the same position in the protein as in native bacteriorhodopsin. This points out that care should be taken, when bleached bacteriorhodopsin is reconstituted with different retinal analogs.     

Effects of different alkali metal ions on the cationization of poly(ethylene glycol)s in matrix-assisted laser desorption/ionization mass spectrometry: a new selectivity parameter

The cationization of poly(ethylene glycol)s, PEG 4000 and PEG 6000, under matrix-assisted laser desorption/ionization conditions was studied by using different concentration ratios of the sodium ion, as the reference ion, and another alkali metal ion (Li(+), K(+), Rb(+), Cs(+)). A linear correlation was found between the intensity ratio of the sodiated PEGs and PEGs cationized with alkali metal ions versus the initial concentration ratio of sodium and alkali metal ions. The slopes of these straight lines are proposed as a novel selectivity ratio for the ionization process. The intensity distribution of the cationized PEGs was also investigated. It was found that the cationized oligomers follow Poisson statistics. The M(n) and M(w) values were also evaluated. An explanation for the observed effects is given.