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W Kaminsky

Publications and source records attributed to W Kaminsky.

9 recordsLinked to original sources
PubMed2001

C--N bond formation on addition of aryl carbanions to the electrophilic nitrido ligand in TpOs(N)Cl(2).

The osmium(VI) nitrido complex TpOs(N)Cl(2) (1) has been prepared from K[Os(N)O(3)] and KTp in aqueous ethanolic HCl. It reacts rapidly with PhMgCl and related reagents with transfer of a phenyl group to the nitrido ligand. This forms Os(IV) metalla-analido complexes, which are readily protonated to give the analido complex TpOs(NHPh)Cl(2) (4). The nitrido-phenyl derivatives TpOs(N)PhCl and TpOs(N)Ph(2) react more slowly with PhMgCl and are not competent intermediates for the reaction of 1 with PhMgCl. Reactions of 1 with alkyl- and arylboranes similarly result in transfer of one organic group to nitrogen, leading to isolable borylamido complexes such as TpOs[N(Ph)(BPh(2))]Cl(2) (11). This is an unprecedented insertion of a nitrido ligand into a boron--carbon bond. Hydrolysis of 11 gives 4. Mechanistic studies suggest that both the Grignard and borane reactions proceed by initial weak coordination of Mg or B to the nitrido ligand, followed by migration of the carbanion to nitrogen. The hydrocarbyl group does not go to osmium and then move to nitrogen--there is no change in the atoms bound to the osmium during the reactions. It is suggested that there may be a general preference for nucleophiles to add directly to the metal--ligand multiple bond rather than binding to the metal first and migrating. Ab initio calculations show that the unusual reactivity of 1 results from its accessible LUMO and LUMO + 1, which are the Os = N pi* orbitals. The bonding in 1 and its reactivity with organoboranes are reminiscent of CO.

Journal Article↗
PubMed2001

Why is there an "inert" metal center in the active site of nitrile hydratase? Reactivity and ligand dissociation from a five-coordinate Co(III) nitrile hydratase model.

To determine how a substitutionally inert metal can play a catalytic role in the metalloenzyme nitrile hydratase (NHase), a reactive five-coordinate Co(III) thiolate complex ([Co(III)(S(2)(Me2)N(3)(Pr,Pr))](PF(6)) (1)) that resembles the active site of cobalt containing nitrile hydratase (Co NHase) was prepared. This was screened for reactivity, by using low-temperature electronic absorption spectroscopy, toward a number of biologically relevant "substrates". It was determined 1 will react with azide, thiocyanate, and ammonia, but is unreactive toward nitriles, NO, and butyrate. Substrate-bound 1 has similar spectroscopic and structural properties as [Co(III)(ADIT(2))](PF(6)) (2). Complex 2 is a six-coordinate Co(III) complex containing cis-thiolates and imine nitrogens, and has properties similar to the cobalt center of Co NHase. Substrate binding to 1 is reversible and temperature-dependent, allowing for the determination of the thermodynamic parameters of azide and thiocyanate binding and the rates of ligand dissociation. Azide and thiocyanate bind trans to a thiolate, and with similar entropies and enthalpies (thiocyanate: DeltaH = -7.5 +/- 1.1 kcal/mol, DeltaS = -17.2 +/- 3.2 eu; azide: DeltaH = -6.5 +/- 1.0 kcal/mol, DeltaS = -12.6 +/- 2.4 eu). The rates of azide and thiocyanate displacement from the metal center are also comparable to one another (k(d) = (7.22 +/- 0.04) x 10(-)(1) s(-)(1) for thiocyanate and k(d) = (2.14 +/- 0.50) x 10(-)(2) s(-)(1) for azide), and are considerably faster than one would expect for a low-spin d(6) six-coordinate Co(III) complex. These rates are comparable to those of an analogous Fe(III) complex, demonstrating that Co(III) and Fe(III) react at comparable rates when in this ligand environment. This study therefore indicates that ligand displacement from a low-spin Co(III) center in a ligand environment that resembles NHase is not prohibitively slow so as to disallow catalytic action in nonredox active cobalt metalloenzymes.

Azides↗
PubMed2001

Environmentally compatible polymerization of olefins by the use of metallocene catalysts.

Polyolefins belong to the most non-polluting mass polymers since they consist of carbon and hydrogen, only. Additionally the pure polymers can be easily reused, they can be decomposed into their monomer building blocks or they can be burned to carbon dioxide and water under production of energy. With metallocene catalysts the efficiency of the polymerization compared to the common "Ziegler-Natta" catalysts can be increased by the factor of 10-100. Therefore, resources are saved and energy costs decreased. The metallocene catalysts allow in a so far unknown fashion the synthesis of polymers in a very distinctive way. By variation of the ligand structure it is possible to influence as well the microstructure of the polymers as the stereo- and regio-selectivity and the tacticity in a broad range. Therefore, the production of polymers with outstanding mechanical properties becomes possible, so far these were reserved for high-performance polymers, which can be only made with high efforts and less environmentally compatible.

Alkenes↗
PubMed2001

Pyrolysis of oil sludge in a fluidised bed reactor.

The oil sludge of tanker cleaning was pyrolysed in fluidised bed reactors. Three experiments were conducted in a laboratory plant and two on a technical plant. Separation of oil from the solids and distribution of the oil products were investigated at temperatures from 460 degrees C to 650 degrees C. Between 70% and 84% of the oil could be separated from the solids. Distribution of the oil products depended on the feed material and the pyrolysis conditions. The higher the temperature the more the oil was cracked into low boiling compounds. Under the conditions of pyrolysis carbon reduced gridiron to iron. Thus some solid fractions were pyrophoric and oxidised with high heat generation. Therefore the solid products have to be turned into inert substances. The fluidised bed pyrolysis is an adequate process to recycle oil sludge with high yields.

Carbon↗
PubMed2000

Images of absolute retardance L.Deltan, using the rotating polariser method

Modulation techniques for measuring changes in optical birefringence, such as the rotating-polariser method (Wood & Glazer, 1980, J. Appl. Crystallogr. 13, 217), allow one to determine |sin delta|, delta = 2piLDeltan/lambda, Deltan = double refraction, L = light path and lambda = wavelength. However, they generally suffer from not providing absolute values of the optical retardance or are limited to relatively low retardance values. In addition, knowledge of the absolute phase is required when establishing the correct values of optical orientation information. In this paper, it is shown how the phase delta, and thus optical retardance, can be extracted from combining measurements of |sin delta| at different wavelengths. The new approach works on each single point of a 2-D picture without the need to correlate with neighbouring points. There is virtually no limit to the retardance, and the computational efforts are small compared with other methods (e.g. Ajovalasit et al. 1998, J. Strain Analysis 33, 75). When used with imaging techniques, such as the rotating polariser method of Glazer, Lewis & Kaminsky 1996 (Proc. R. Soc. London Series A452, 2751) this process has the potential to identify automatically optically anisotropic substances under the microscope. The algorithm derived in this paper is valid not only for birefringence studies, but can be applied to all studies of interfering light waves.

Journal Article↗
PubMed2000

New Pathways in Plastics Recycling.

The catalytic degradation of polyethylene to short-chain hydrocarbons is possible with zirconium hydride compounds (see picture), and represents the first step in the reversal of Ziegler - Natta polymerization. Thus, even in the case of polyolefins the important target of plastics recycling, the recovery of reusable monomers from polymer waste, may be achieved.

Journal Article↗