Efficient asymmetric hydrogenation with rhodium complexes of C(1)-symmetric 2,5-dimethylphospholane-diphenylphosphines

The unsymmetrical, optically active ligands 1,2-C(6)H(4)(PPh(2))((R,R)-2,5-dimethylphospholanyl) and the new 1,1'-Fe(C(5)H(4))(2)(PPh(2))((R,R)-2,5-dimethylphospholanyl) form complexes of the type [PtCl(2)(diphos)] and [Rh(diphos)(diene)][BF(4)]. The crystal structure of reveals that only one quadrant is blocked. Asymmetric hydrogenation of acrylic esters and enamides using and as catalysts show that the phenylene-backboned diphosphine gives a more efficient catalyst in terms of asymmetric induction than the more flexible ferrocene-backboned diphosphine. The best results, which were obtained with and enamide substrates, exceeded those obtained with Duphos catalysts. The rate of hydrogenation of the enamides with was 10 times faster than with [Rh(Duphos)(diene)][BF(4)]. A quadrant diagram can be used to predict the configuration of the major product, provided it is assumed to be derived from the less sterically congested intermediate.     

Bifunctional chelators for copper radiopharmaceuticals: the synthesis of [Cu(ATSM)-amino acid] and [Cu(ATSM)-octreotide] conjugates

Two new bifunctional chelators that are derivatives of the bis(thiosemicarbazone) ATSMH(2) proligand have been prepared, one with two phenyl carboxylate substituents on the exocyclic nitrogens (L(1)H(2)) and one with a single phenyl carboxylate (L(2)H(2)). The new ligands have been characterised by NMR spectroscopy, mass spectrometry and in the case of L(1)H(2) by X-ray crystallography. The copper, nickel and zinc complexes of the new ligands have been synthesised and characterised. Electrochemical measurements show that the copper(II) complexes undergo a reversible reduction attributable to a Cu(II)/Cu(I) process. The new proligands have been tethered to the N-alpha-Boc-protected amino acids lysine and ornithine using solution and solid phase methods. The new amino acid conjugates form copper complexes and the complexes have been characterised by mass spectrometry and electronic spectroscopy. The bifunctional chelator L(2)H(2) has been conjugated to the tumour targeting peptide octreotide and the new ATSMH(2)-octreotide conjugate and its copper complex have been characterized by mass spectrometry. These new systems have the potential to be used for new targeted copper radiopharmaceuticals for imaging and therapy.     

The effect of arsenate,and of transitioń-metal ions,on the precipitation of phosphate as ammonium 12-molybdophosphate

The radionuclides phosphorus-32, arsenic-74, iron-59 and molybdenum-99 were used to determine the effect-of arsenate and some transition-metal ions on the precipitation of phosphorus as ammonium 12-molybdophosphate. Under the conditions necessary for the quantitative precipitation of phosphorus, arsenic is also precipitated by ammonium molybdate. The presence of iron(III) nitrate inhibits the precipitation of phosphorus and, particularly, arsenic, although the precipitates contain more molybdenum, and are heavier, than when iron is absent. Chromium (111) nitrate, nickel(II) nitrate and manganese(II) nitrate do not inhibit the precipitation of phosphorus and arsenic to the same extent as iron (III) nitrate.     

2,2′-Bis((di-tert-butylphosphino)methyl)-1,1′-biphenyl (ditbi): a bulky analogue of bisbi. The crystal structure of [Rh2Cl2(1,5-cod)2(μ-ditbi)]

Diphosphine 2,2′-bis(di-tert-butylphosphino)methyl)-1,1′-biphenyl (ditbi) is synthesised by the addition of to 2,2′-bis(bromomethyl)-1,1′-biphenyl, followed by deprotection with diethylamine. Treatment of [Rh₂Cl₂(1,5-cod)₂], with ditbi gives [Rh₂Cl₂(1,5-cod)₂(μ-ditbi)] (2) as confirmed by its X-ray crystal structure determination. Hydroformylation of 1-hexene using [Rh(acac)(CO)₂]/ditbi as catalyst gave n- and iso-heptanal in a ratio of 1:1.     

New experimental method for the determination of single-component isotherms: an application of the flow-rate retention time

In this paper, we investigate adsorption of a single component (refrigerant) from the variation in the flow rate leaving the column. This requires evaluation of the flow-rate retention time—a measure of the net change in the amount adsorbed in the column, which can be positive or negative. The arrangement includes a system to deliver a fixed flow (30 mL/min) of helium through a column packed with 0.05 g of adsorbent. An experiment is initiated by adding a flow of refrigerant to the helium, and monitoring the outlet flow rate from the column. There are two main advantages of this approach: the experimental times are short (the order of 10 minutes) and the sensitivity is very high so that it can be used with very small as well as large amounts of adsorbent. Indeed, a sensitivity analysis suggests that the resolution is of the order of 10^?5 g. The first results section considers the corrections required to the measured flow-rate retention time—these are small and determined by empty volume in the system. The second results section involves a determination of the adsorption isotherm of HFC-134A on an activated carbon at 35?°C up to a partial pressure of 0.25 bar.