Recent studies on phosphorus-bridging carbonyl derivatives: organophosphorus analogs of aldehydes and ketones

Reactions of disodium tetracarbonylferrate, Na₂Fe(CO)₄, with sterically hindered dialkylaminodichlorophosphines, R₂NPCl₂ (R₂N=diisopropylamino, dicyclohexylamino, and 2,2, 6, 6-tetramethylpiperidino) in diethyl ether lead to the air-stable phosphorus-bridging carbonyl derivatives (R₂NP)₂COFe₂(CO)₆ as the major products. The phosphorus-bridging carbonyl group in (i-Pr₂NP)₂COFe₂(CO)₆ has been found to undergo the following types of reactions: 1)Reduction, 2)Acylation, 3)Extrusion of the carbonyl group. The mechanisms of the reactions have been considered.This work was presented at the Workshop «The Modern Problems of Heteroorganic Chemistry» held on the ship «Nikolai Bauman» during the period May 8–13, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1858–1867, November, 1993.     

Convergence of interval-type algorithms for generalized fractional programming

The purpose of this paper is to analyze the convergence of interval-type algorithms for solving the generalized fractional program. They are characterized by an interval [LB _k , UB _k ] including*, and the length of the interval is reduced at each iteration. A closer analysis of the bounds LB _k and UB _k allows to modify slightly the best known interval-type algorithm NEWMODM accordingly to prove its convergence and derive convergence rates similar to those for a Dinkelbach-type algorithm MAXMODM under the same conditions. Numerical results in the linear case indicate that the modifications to get convergence results are not obtained at the expense of the numerical efficiency since the modified version BFII is as efficient as NEWMODM and more efficient than MAXMODM.This research was supported by NSERC (Grant A8312) and FCAR (Grant 0899).     

X-ray structure and UV spectroscopic studies of (adenmato-N9)triethylphosphinegold(I)

The preparation, characterization, and X-ray structure analysis of (adeninatoN9)triethylphosphinegold(I) is reported. The crystal structure consists of discrete molecules, the adeninate anion coordinates via the N(9) atom with a Au-N(9) bond distance of 2.057(5) Å and the linear geometry about the Au atom is completed by the P atom of a disordered Et₃P ligand; the Au-P(1) bond distance is 2.238(2) Å and the N(9)-Au-P(1) bond angle is 178.8(2)°. The crystals are orthorhombic, space groupPbca, with unit cell dimensionsa=8.528(1),b=17.797(3),c=18.526(2) Å andZ=8. The structure was refined by a full-matrix least-squares procedure to finalR=0.030 andR _w =0.033 for 1749 reflections withI>2.5a(I). The electronic spectrum of the complex dissolved in water in the near ultraviolet is consistent with essentially separate -electron systems of the adenine and phosphinegold moieties; a conclusion which corroborates the X-ray structural results.     

Synthesis of 3-formyltetronic acid and enamine derivatives

The first reported synthesis of 3-formyltetronic acid and its conversion to enamine derivatives is described. 3-Dimethylaminomethylene-2,4-dioxotetrahydrofuran derivatives were also prepared by treatment of tetronic acids with dimethylformamide diethyl acetal. Nmr spectral studies are included.