In recent years, research in organophosphorus chemistry has mainly focused in designing newer and better phosphorus ligands for synthesizing novel metal complexes with improved catalytic activities. Aminophosphines [tricoordinate phosphorus(III)–nitrogen systems] are considered as versatile compounds owing to the presence of nitrogen centres which, in principle, can influence additional reactivity features. They are quite sensitive to air and moisture due to the presence of polar PN bond(s). In spite of this, research in aminophosphine chemistry is gaining momentum day-by-day and this is due mainly to one reason: their rich behaviour as ligands in metal complex chemistry and subsequently in catalysis. Their role as synthons in inorganic heterocyclic chemistry has also helped produce new types of heterocycles. In this paper, the chemistry of simple acyclic aminophosphines (synthesis, characterization, reactivity and applications) is covered and particular focus is given to their ability to form chalcogenides along with their role played as ligands in coordination chemistry and as synthons in inorganic heterocyclic chemistry. Copyright © 2009 John Wiley & Sons, Ltd.

Aminophosphines: their chemistry and role as ligands and synthons

Strukturänderungen während der Oxidation B‐, C‐, Si‐ oder P‐substituierter Hydrazine

The two-photon photochemistry of CdSe quantum dots (QDs) has been systematically studied. We find that upon intense irradiation CdSe quantum dots that absorb two or more visible photons undergo photodarkening. The quantum yield for this process is on the order of 6% in chloroform and much smaller in nonpolar solvents, such as octane. An analysis of the energetics indicates that, following two-photon excitation, the biexciton undergoes an Auger process producing a hot hole. This hot hole is ejected to a surface-bound TOP ligand, forming a QD–/TOP+ contact ion pair that separates in chloroform, but not in octane. The charged and deligated QD is dark, resulting in the overall photodarkening. This photodarkening reaction may or may not be reversible, depending on what other chemical components are in the irradiated solution. The quantum dot concentration dependence and PL decay kinetics indicate that charge recombination occurs rapidly, followed by ligand reattachment and reorganization on a longer (tens of m...

Two-Photon Photochemistry of CdSe Quantum Dots

Zinndichlorid und Zinndibromid reagieren mit Tri-tert-butylphosphin und mit Tris(dimethylamino)phosphin zu stabilen 1:1-Addukten. Die Bindungsverhaltnisse dieser neuen ylidartigen Phosphindihalogenstannylene werden anhand von IR-, Raman-, 1H-NMR-, 31P-NMR- und 119mSn-Mosbauerspektren diskutiert.



Tin(II) Halide Complexes with Tri-tert-butylphosphine and Tris(dimethylamino)-phosphine



TIn(II) chloride and tin(II) bromide react with tri-tert-butylphosphine and with tris(dimethylamino)phosphine to give stable 1:1 adducts. Infrared and raman data as well as1H-n.m.r., 31P-n.m.r., and 119mSn-Mossbauer spectra of the novel phosphine dihalogennostannylenes are discussed in terms of an ylidic type of bonding.

N. A. Kuebler

Papers

Molecular photoelectron spectroscopic investigation of some caged phosphorus compounds and related acyclic species

Molecular photoelectron spectroscopic investigation of some caged phosphorus compounds and related acyclic species