Magnetic resonance studies of metal–olefin complexes. I. Electron spin resonance spectra of γ-irradiated silver perchlorate cycloalkene complexes

Gee, D. R.; Russell, K. E.; Wan, J. K. S.

doi:10.1139/v70-462

Cited by 9 publications

(5 citation statements)

References 13 publications

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“…Again this indicates that little ring distortion occurs in the complexed radical. The derived spin density of 3.0 + 0.3 % on the silver ion of the silver cyclohexadienyl radicals compares with the value of 3.4% estimated for silver cyclohexenyl radical (8). This suggests that some small weakening of the coordinate bond occurs probably as a result of the conjugation in the cyclodienyl system.…”

Section: Silver Cyclol~exadienyl Radicalssupporting

confidence: 61%

“…spectra observed when silver perchlorate 1-methyl-cyclopentene complex was irradiated almost certainly results from Ag+ I-methyl-3-cyclopentyl radical (8). Computer analysis of the experimental spectra on this basis yields the parameters presented in Table 1.…”

Section: Resultsmentioning

confidence: 96%

“…Silver analyses of all these complexes were within 0.02% of the values predicted. Sample irradiation has been described previously (8 …”

Section: Methodsmentioning

confidence: 99%

“…As a parallel study to silver olefin complexes, we have initiated a systematic investigation of silver alkenyl radicals generated by y-irradiation of the parent complexes (7)(8)(9). In the present report we have extended our studies of silver alkenyl radicals to include silver l-methylcyclopentenyl radical and the corresponding uncomplexed 1-methyl-cyclopentenyl radical, the silver cyclohexadienyl radicals generated from the 1,3-and 1,4-cyclohexadiene silver perchlorate and silver tetrafluoroborate complexes.…”

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confidence: 99%

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Magnetic Resonance Studies of Metal Olefin Complexes. II. Electron Spin Resonance Spectra of γ-Irradiated Silver Complexes with Cyclohexadienes and 1-Methyl Cyclopentene

Gee¹,

Wan²

1971

Can. J. Chem.

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Section: Silver Cyclol~exadienyl Radicalssupporting

confidence: 61%

Section: Resultsmentioning

confidence: 96%

“…Silver analyses of all these complexes were within 0.02% of the values predicted. Sample irradiation has been described previously (8 …”

Section: Methodsmentioning

confidence: 99%

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confidence: 99%

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Magnetic Resonance Studies of Metal Olefin Complexes. II. Electron Spin Resonance Spectra of γ-Irradiated Silver Complexes with Cyclohexadienes and 1-Methyl Cyclopentene

Gee¹,

Wan²

1971

Can. J. Chem.

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“…Silver -cycloalkenyl radicals have been observed in y-radiolysis of solid silver cycloalkene complexes (10,11). Similar photochemical behavior was observed for the polycyclic silver -P-pinene and silver -apinene complexes.…”

supporting

confidence: 56%

Photochemistry of Metal Olefin Complexes. Isomerization and Stereospecific Cyclodimerization of Silver Cycloalkene Complexes

Leh¹,

Wong²,

Wan³

1971

Can. J. Chem.

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PhotoIysis of AgCI04 -1-methylene cyclohexane complex in pure polycrystalline state or in methanol solution leads to isomerization of the complex to AgCIO4 -1-methylcyclohexene. The isomerized complex undergoes further photochemical cyclodimerization giving the stereospecific exo-trans-exo dimer of the 1-methylcyclohexene and colloidal silver. Similar photoisomerization and a less stereospecific photodimerization were observed in the photolysis of the polycyclic AgC104 -p-pinene complex.La photolyse du complexe mtthylene-1 cyclohexane -AgCIO, soit sous forme polycristalline soit en solution dans le mtthanol conduit B une isomtrisation du complexe en mtthyl-1 cyclohexene -AgClO,.Le complexe isomtrist subit une cyclodimtrisation photochimique ulttrieure pour donner d'une f a~o n sttrtosptcifique le dimere exo-trans-exo du mtthyl-1 cyclohexene et de I'argent collofdal. De la mdme f a~o n , une photoisomtrisation et une photodimtrisation moins sttrtospecifique sont observtes dans la photolyse du complexe polycyclique P-pinhe -AgCIO4.Canadian Journal of Chemistry. 49, 2760 (1971) Although recent interests in the Agf-catalyzed rearrangements of strain polycyclic alkanes are developing rapidly (1-6), surprisingly little effort has been devoted to explore the photochemical reactivity of the well-known silver-olefin complexes. We report here the photoisomerization and the stereospecific photocyclodimerization of AgC10, complexes of 1-methylene cyclohexane and 1-methylcyclohexene. Similar photochemical reactions of the silver -P-pinene complex are also observed. These results indicate that the photochemical reactivity of these silver-olefin complexes are distinctly different from those of the free ligands and may be of general interest to synthetic and mechanistic organic photochemistry.The complexes were prepared by addition of the corresponding olefins to an acetone solution of AgC10, at 0 "C. The white crystalline products were filtered, washed, and dried over P205. Silver analyses of these solid complexes indicated a 2:l olefin to Ag ratio. Since the i.r. and n.m.r. data characterizing these complexes are not available in the literature, they are presented here in Table 1.The AgClO, -I-methylene cyclohexane complex was found to be stable in the dark at 0 "C for several weeks. Irradiation of a methanol solution of this complex (0.1 M) with U.V.(2537 A) effects firstly an isomerization to silver -1-methylcyclohexetle. The photoisomerization can be readily followed by n.m.r. and/or i.r. analyses showing the conversion of a complexed exocyclic olefin to a complexed endocycloalkene. The rate of the photoisomerization process is apparently independent of temperature within the range 10-30 "C. However, photolysis of the complex in the pure solid state leads to a tenfold increase in the rate of conversion. Prolonged irradiation of the complex either in solution or in the solid state for several hours results in secondary photochemical reaction of the isomer product giving the sole exo-trans-exo cyclic dimer of the 1-rnethy...

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Application of Electron Spin Resonance Spectroscopy to Photochemistry

Wan

1974

Advances in Photochemistry

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Magnetic resonance studies of metal–olefin complexes. I. Electron spin resonance spectra of γ-irradiated silver perchlorate cycloalkene complexes

Cited by 9 publications

References 13 publications

Magnetic Resonance Studies of Metal Olefin Complexes. II. Electron Spin Resonance Spectra of γ-Irradiated Silver Complexes with Cyclohexadienes and 1-Methyl Cyclopentene

Magnetic Resonance Studies of Metal Olefin Complexes. II. Electron Spin Resonance Spectra of γ-Irradiated Silver Complexes with Cyclohexadienes and 1-Methyl Cyclopentene

Photochemistry of Metal Olefin Complexes. Isomerization and Stereospecific Cyclodimerization of Silver Cycloalkene Complexes

Application of Electron Spin Resonance Spectroscopy to Photochemistry

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