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I. Photochemical cycloaddition and solvent addition reactions of metal ion-alkene complexes. II. Syntheses, reactivity patterns, and thermodynamic properties of actinide alkyls and metallacycles

Thesis/Dissertation ·
OSTI ID:5675438
Irradiation of norbornene complexes of Cu(I), Cu(II), or Ag(I) trifluoromethanesulfonates in ethereal solvents results in catalytic cycloaddition of alkene. In acetonitrile, irradiation of norbornene complexes of Ag(I) or Tl(I) triflates yields 2-(cyanomethyl)-bicyclo(2,2,1)heptane in good yield. Mechanistic studies indicate that the primary photoprocess is alkene to metal electron transfer, yielding the alkene radical cation. This radical cation abstracts a hydrogen atom from solvent molecule, generating .CH/sub 2/X (X = CN, OH) which initiates a radical chain addition to alkene. Actinide organometallics of general formula (C/sub 5/Me/sub 5/)/sub 2/MR/sub 2/ are generally available from (C/sub 5/Me/sub 5/)/sub 2/MCl/sub 2/ and lithium alkyls. Reactivity studies have revealed several interesting tendencies. For R groups with extensive branching at the ..beta..-carbon, thermolysis leads to a ..gamma.. C-H activation and metallacycle formation. This process was extensively studied by kinetic and deuterium labelling methods. The metallacycle is highly reactive in intermolecular C-H activation processes, but not in metathesis or polymerization. Titration calorimetric studies were employed to develop an extensive series of metal-ligand bond strengths. These are useful in calculating enthalpy changes for observed and proposed reactions, and they indicate the high thermodynamic stability of actinide organometallics.
Research Organization:
Northwestern Univ., Evanston, IL (USA)
OSTI ID:
5675438
Country of Publication:
United States
Language:
English

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Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600 -- Radiation Chemistry
400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPLEXES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
COPPER COMPLEXES
DATA
DECOMPOSITION
DEUTERIUM COMPOUNDS
ELECTROMAGNETIC RADIATION
ENTHALPY
EXPERIMENTAL DATA
GAMMA RADIATION
HYDROGEN COMPOUNDS
INFORMATION
IONIZING RADIATIONS
LABELLING
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHYSICAL PROPERTIES
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RADIOLYSIS
SILVER COMPLEXES
SULFONATES
TEMPERATURE EFFECTS
THALLIUM COMPLEXES
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPLEXES