The electronic structure of benzvalene : Photoelectronspectroscopic studies

The photoelectron(PE)spectrum of tricyclo[3.1.0.0^2,6] hex-2-ene(benzvalene 1) has been recorded. The first four bands in the PE spectrum of 1 can be assigned to transitions to ²B₂, ²A₁, ²A₂ and ²B₁ states of 1¹. This assignment is discussed in terms of the results of semiempirical and ab initio calculations on 1. Furthermore the highest occupied MO's of 1 are derived qualitatively from an interaction diagram between a distorted bicyclobutane and an ethylene moiety.     

Cis di-oxomolybdenum(VI) complexes with a tridentate ONO donor ligand; synthesis,X-ray crystal structure,spectroscopic properties and oxotransfer chemistry

The molybdenum complexes of Schiff base ligands viz. [MoO₂LH₂O] where L¹ = tris(hydroxymethyl)(salicylide-neamino)methane, L² = tris(hydroxymethyl)(2,3-dihydroxybenzylideneamino)methane and L³ = tris(hydroxymethyl)(2,3,4-trihydroxybenzylideneamino)methane have been synthesized and characterized by spectroscopic and electrochemical techniques. The X-ray crystal structure of the complex [MoO₂L¹H₂O] reveals a distorted octahedral geometry with one ligand and a water molecule coordinated to the MoO₂ center. No previous complex of this type contains a coordinated water molecule. The complex undergoes an oxotransfer in the presence of Bu₃P to form a -oxobridged molybdenum(V,V) dimer. This rules out Mo—S coordination as a prerequisite for oxotransfer in such molybdenum(VI) complexes.     

Determination of selenium in blood serum by ICP-OES including an on-line wet digestion and Se-hydride formation procedure

Summary An analytical procedure for the determination of Se, as well as of other trace elements of clinical interest, in undiluted blood serum samples is presented. This procedure allows the on-line wet ashing of the sample, the hydride generation and the determination of the SeH₂ formed in one step. For this purpose, carrier solution and the injected sample (300 l) were merged with an acid stream (80% H₂SO₄, 12% HClO₄, 8% HNO₃) and passed through a reaction coil heated up to 240°C. To increase the dispersion, the wet digestion was carried out in an ultrasonic field. After trapping of the gas bubbles, 5 mol/l HCl and 0.053 mol/l NaBH₄ solutions were added via T-junctions for Se-hydride generation. The nebulizing system of the ICP-OES was used as gas/liquid separator. The hydride was swept from the spray chamber into the plasma by an argon gas flow with droplets containing other sample constituents. This allows the simultaneous determination of other trace elements of clinical interest, for example Fe, Cu and Zn. The relative detection limit for Se in blood serum was 5 g/l. The quality of the developed procedure was verified in two ways: by measuring SRM Seronorm 116 and by comparing the results for different serum samples with the results obtained with ETAAS. Our results were in good agreement in both cases.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday