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- W51179517 abstract "In many senses, the hydrogen-atom transfer reactionsobserved with the triplet excited state of pyrophosphito-bridgedplatinum(II) dimers resemble the reactions of organic ketone nπ*states. The first two chapters describe our attempts to understandthe reactivity differences between these two chromophores.Reactivity of the metal dimers is strongly regulated by the detailednature of the ligands that ring the axial site, the hydrogen-abstractioncenter. A hydrogen-bonded network linking the ligandsfacilitates H-atom transfer quenching with alcohols through theformation of a hydrogen-bonded complex between the alcohol and adimer. For substrates of equal C-H bond strength that lack a hydroxylgroup (e.g., benzyl hydrocarbons), the quenching rate is severalorders of magnitude slower. The shape and size of the axial site, as determined by theligands, also discriminate among quenchers by their stericcharacteristics. Very small quenchers quench slowly because of highentropies of activation, while very large ones have large enthalpicbarriers. The two effects find a balance with quenchers of just theright size. The third chapter discusses the design of a massspectrometer that uses positron annihilation to ionize neutralmolecules. The mass spectrometer creates positron-moleculeadducts whose annihilation produces fragmentation products thatmay yield information on the bonding of positrons in such complexes." @default.
- W51179517 created "2016-06-24" @default.
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- W51179517 date "1990-01-01" @default.
- W51179517 modified "2023-09-23" @default.
- W51179517 title "Hydrogen-Atom Transfer Photochemistry of Tetrakis(µ-pyrophosphito)diplatinate(II)" @default.
- W51179517 hasPublicationYear "1990" @default.
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