Transition metal ion complexes of thiosemicarbazones derived from 2-acetylpyridineN-oxide. I. The 4-methyl derivative

Summary TheN-methyl-2-[1-(2-pyridinyl-1-oxide)ethylidene]hydrazinecarbothioamide, HLO4M, has been used to prepare a series of Co^III, Ni^II and Cu^II complexes. Species with two deprotonated LO4M ligands, one LO4M and one HLO4M ligand, two HLO4M ligands and one HLO4M ligand with two small anionic ligands have been isolated. The deprotonated LO4M bonds as a tridentate ligandvia theN-oxide oxygen, the imine nitrogen (N¹ and the sulphur while the HLO4M ligand coordinates primarily as a bidentate ligandvia only the first two atoms listed above. I.r., electronic, mass and e.s.r. spectra have been used to determine the nature of these complexes. One of the more striking differences between these compounds and those prepared with other thiosemicarbazones of 2-acetylpyridine and 2-acetylpyridineN-oxide is that tetrahedral yellow [Ni(HL)X₂] rather than planar brown [NiLX] (X=Cl or Br) solids have been isolated with this ligand. Other differences in the nature of the coordination spheres of the various metal ions occur with this particular ligand when compared to previously studied thiosemicarbazone complexes.NATO Fellow, on leave from Medical Faculty, Istanbul University.     

A novel,stereoselective silyl-directed Stevens [1,2]-shift of ammonium ylides

[reaction: see text] The silyl group of 2-silylpyrrolidines such as 1 plays several critical roles: a stereochemical control element in a facially selective carbenoid addition to the ring nitrogen, a stereochemical "placeholder" during regioselective 1,2-migration with retention by the resulting spirocyclic ammonium ylide, and a hydroxyl surrogate for an eventual stereoselective Fleming-Tamao oxidation. This chemistry represents a novel use of the Stevens rearrangement and offers a short, enantioselective route to hydroxylated quinolizidines such as 3 from Boc-pyrrolidine.     

N-butyl-,N-iso-butyl-andN-sec-butyl-2-picolinamineN-oxide complexes derived from copper(II) salts of polyatomic anions

Summary N-butyl-,N-iso-butyl- andN-sec-butyl-2-picolinamineN- oxide complexes have been prepared from copper(II) perchlorate, tetrafluoroborate and nitrate. Violet solids were isolated from the first two salts while complexes isolated from the nitrate salt were blue green or blue. The ligands coordinatevia both theN-oxide oxygen and the amine nitrogen to give bis (ligand) complexes and only in the case of the nitrate solids is there interaction between the copper(II) centre and the polyatomic anion. Resolution of the g feature in the powder spectra of several of these complexes results from the bulkiness of the butyl groups and therefore dilution of the copper(II) centers. In comparison to the previously studied 2 picolinamineN-oxides with lower alkyl substituents, the complexes have stronger in-plane bonding by the ligands.NATO Fellow on leave from Istanbul Medical Faculty, Istanbul University.     

An investigation of some experimental parameters in atomic fluorescence spectrophotometry

Atomic fluorescence in flames is measured by an adaptation of a commercially available flame spectrophotometer. A study is reported of the effect of background radiation and source scattering on 3 flames, air-propane, air-hydrogen and air-acetylene, and of the effects of variation of fuel gas pressure, zone of measurement in the flame, analysing monochromator slit-width and wavelength of measurement. The air-propane flame appears to offer several advantages. The atomic fluorescence of 10 metals is described; those of Co, Fe and Mn have not been previously reported. Excitation of spectra is achieved by means of an a.c. xenon arc lamp or individual discharge lamps.     

Relaxed chromatic numbers of graphs

Given any family of graphsP, theP chromatic number _p (G) of a graphG is the smallest number of classes into whichV(G) can be partitioned such that each class induces a subgraph inP. We study this for hereditary familiesP of two broad types: the graphs containing no subgraph of a fixed graphH, and the graphs that are disjoint unions of subgraphs ofH. We generalize results on ordinary chromatic number and we computeP chromatic number for special choices ofP on special classes of graphs.Research supported in part by ONR Grant N00014-85K0570 and by a grant from the University of Illinois Research Board.