Trimethylsilyl- and trimethylstannyldimethylphosphane--convenient and versatile reagents for the synthesis of polyfluoroaryldimethylphosphanes.
Trimethylsilyldimethylphosphane (Me3SiPMe2) and the corresponding tin compound (Me3SnPMe2) were used as reagents for the substitution of fluorine by the Me2P group in polyfluoroarenes C6F5X (X = F, H, Cl, CF3) and C5NF5. The reactions occur even under mild conditions (T = 0-20 C), either in benzene or without solvent, to give as a rule 4-X-1-(dimethylphosphano)tetrafluorobenzenes (XC6F4PMe2, 1-4) and 4-(dimethylphosphano)tetrafluoropyridine (C5NF4PMe2, 5), respectively, in yields between 75 and 95%. In the case of C6F6, double substitution is also observed, which affords 1,4-bis(dimethylphosphano)tetrafluorobenzene (6). A very efficient route to the compounds XC6F4PMe2 (X = F, H, Cl, CF3) and C5NF4PMe2 was developed as a one-pot reaction of the corresponding fluoroarenes with tetramethyldiphosphane (P2Me4) and trimethyltin hydride (Me3SnH) at moderate temperatures. This process was tested for C6F6 and perfluorobiphenyl which gave C6F5PMe2 (1) and 4,4'-bis(dimethylphosphano)octafluorobiphenyl (7), respectively. The results, which included kinetic measurements that used the intensities of the 31P signals, revealed the influence of the substrate type on the rate of reaction in the sequence: C5NF5>C6F5CF3> C6F5Cl, C6F5PMe2>C6F5H>C6F6>> C6H5F. Ab initio calculations were carried out on the model reactions of pentafluoropyridine with silylphosphane, phosphane or phosphide to discriminate between possible reaction mechanisms. The novel phosphanes were characterised by spectroscopic investigations (NMR, MS), by preparation of the related thiophosphanes ArFP(=S)Me2 (8-14), their spectroscopic and analytic data and single crystal X-ray diffraction studies on five of these derivatives.
Frustrated Lewis pairs: reactivities of TMS protected amines and phosphines in the presence of B(C(6)F(5))(3).
TMS protected amines in combination with B(C(6)F(5))(3) were found to activate H(2) and this is followed by a cleavage of the N-Si bond and the generation of TMSH. A TMS protected phosphine on the other hand reacts rapidly with B(C(6)F(5))(3) to give the known compound tBu(2)P(C(6)F(4))B(C(6)F(5))(2) by a facile and efficient route.
Physical Processes in Inorganic Scintillators
BASIC PRINCIPLES AND PROCESSES Physical Mechanism of Scintillation Creation of Electron Hole Pairs Excitation and Emission of Luminescence Centers Scintillation Materials Halides Oxides and Oxide Systems Chalcogenides Glasses Interaction of Ionizing Radiation with Scintillators High Energy Photons Charged Particles Neutral Particles General Characteristics of Inorganic Scintillators Light Yield Duration of Scintillation Pulse Afterglow Temperature Response Optical Properties Radiation Hardness Density Emission Spectra Mechanical and Chemical Properties Physical Parameters Cost Consideration Scintillator Requirements in Various Applications High Energy Physics Intermediate Energy Physics Positron Emission Tomography Gamma Spectroscopy Energy Resolution Intrinsic Scintillator Resolution Nonproportional Response Time Resolution Low Energy Quanta and Electrons CONVERSION OF ELECTRONIC EXCITATIONS IN SOLIDS Charge Carrier Behaviors Delta Rays Secondaries Excitation of Luminescence Centers Effect of Ionization Density Energy Losses Simple Phenomenological Model Plasmon Model Polaron Model Scintillation Yield Spectra Vacuum Ultraviolet Region Ultrasoft X-Rays X-Rays Gamma Rays Heavy Ionizing Particles INTRINSIC LUMINESCENCE OF INORGANIC SCINTILLATORS Excitonic Luminescence Alkali Halide Crystals Alkaline-Earth Fluorides Ternary Halide Compounds Excitonic-Like Luminescence Cesium Iodide Tungstate and Molybdate Phosphors Core-to-Valence Transitions First Evidence for Radiative Core-to-Valence Transitions Excitation Spectra Emission Spectra Experiment Theory Luminescence Kinetics Experimental Theoretical Investigations Temperature Dependence of Luminescence Parameters Conditions of Detection Prospects for Research EXTRINSIC LUMINESCENCE OF INORGANIC SCINTILLATORS Thallium-Activated Halide Scintillators Crystals with NaCl-Type Structure Crystals with CsCl-Type Structure Other Thallium-Based and Thallium-Doped Crystals Crystals Containing Other ns2 Ions Bismuth Germanate (BGO) Sodium-Activated Cesium Iodide Rare-Earth-Activated Crystals General Considerations Europium-Activated Crystals Cerium-Activated Compounds Preliminary Comments LaF3-CeF3 Systems Cerium Chloride Barium Fluoride Gadolinium-Containing Crystals Lu- and Y-Containing Crystals Nd- and Pr-Activated Crystals DEFECT FORMATION BY IONIZING RADIATION Effect on Scintillator Characteristics Mechanisms of Defect Formation Efficiency of Defect Production Geometrical Factor Separation between F and H Centers Temperature Dependence of Production Efficiency Role of Halogen Ion Impurities Effect of Cation Impurities Formation Time of F-H Pairs Closing Comments References Index