1.Oxidation of phenyl and hydride ligands of bis(pentamethylcyclopentadienyl)hafnium derivatives by nitrous oxide via selective oxygen atom transfer reactions: insights from quantum chemistry calculations.
Xie H1, Liu C1, Yuan Y1, Zhou T1, Fan T2, Lei Q3, Fang W3. Dalton Trans. 2016 Jan 21;45(3):1152-9. doi: 10.1039/c5dt03264d.
The mechanisms for the oxidation of phenyl and hydride ligands of bis(pentamethylcyclopentadienyl)hafnium derivatives (Cp* = η(5)-C5Me5) by nitrous oxide via selective oxygen atom transfer reactions have been systematically studied by means of density functional theory (DFT) calculations. On the basis of the calculations, we investigated the original mechanism proposed by Hillhouse and co-workers for the activation of N2O. The calculations showed that the complex with an initial O-coordination of N2O to the coordinatively unsaturated Hf center is not a local minimum. Then we proposed a new reaction mechanism to investigate how N2O is activated and why N2O selectively oxidize phenyl and hydride ligands of . Frontier molecular orbital theory analysis indicates that N2O is activated by nucleophilic attack by the phenyl or hydride ligand. Present calculations provide new insights into the activation of N2O involving the direct oxygen atom transfer from nitrous oxide to metal-ligand bonds instead of the generally observed oxygen abstraction reaction to generate metal-oxo species.
2.Determination of ultra-trace amounts of arsenic(III) by flow-injection hydride generation atomic absorption spectrometry with on-line preconcentration by coprecipitation with lanthanum hydroxide or hafnium hydroxide.
Nielsen S1, Sloth JJ, Hansen EH. Talanta. 1996 Jun;43(6):867-80.
A time-based flow-injection (FI) procedure for the determination of ultra-trace amounts of inorganic arsenic(III) is described, which combines hydride generation atomic absorption spectrometry (HG-AAS) with on-line preconcentration of the analyte by inorganic coprecipitation-dissolution in a filterless knotted Microline reactor. The sample and coprecipitating agent are mixed on-line and merged with an ammonium buffer solution, which promotes a controllable and quantitative collection of the generated hydroxide on the inner walls of the knotted reactor incorporated into the FI-HG-AAS system. Subsequently the precipitate is eluted with 1 mol 1(-1) hydrochloric acid, allowing ensuing determination of the analyte via hydride generation. The preconcentration of As(III) was tested by coprecipitation with two different inorganic coprecipitating agents namely La(III) and Hf(IV). It was shown that As(III) is more effectively collected by lanthanum hydroxide than by hafnium hydroxide, the sensitivity achieved by the former being approximately 25% better.
3.Internal dosimetry for inhalation of hafnium tritide aerosols.
Inkret WC1, Schillaci ME, Boyce MK, Cheng YS, Efurd DW, Little TT, Miller G, Musgrave JA, Wermer JR. Radiat Prot Dosimetry. 2001;93(1):55-60.
Metal tritides with low dissolution rates may have residence times in the lungs which are considerably longer than the biological half-time normally associated with tritium in body water, resulting in long-term irradiation of the lungs by low energy beta particles and bremsstrahlung X rays. Samples of hafnium tritide were placed in a lung simulant fluid to determine approximate lung dissolution rates. Hafnium hydride samples were analysed for particle size distribution with a scanning electron microscope. Lung simulant data indicated a biological dissolution half-time for hafnium tritide on the order of 10(5) d. Hafnium hydride particle sizes ranged between 2 and 10 microns, corresponding to activity median aerodynamic diameters of 5 to 25 microns. Review of in vitro dissolution data, development of a biokinetic model, and determination of secondary limits for 1 micron AMAD particles are presented and discussed.