Photoinduced fragmentation of dodecacarbonyltrihydrotrirhenium and dodecacarbonyltrihydrotrimanganese

Epstein, Ronald A.; Gaffney, Thomas R.; Geoffroy, Gregory L.; Gladfelter, Wayne L.; Henderson, Richard S.

doi:10.1021/ja00508a022

Cited by 31 publications

(9 citation statements)

References 10 publications

(17 reference statements)

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“…The 17-electron metal fragments display radical-like reactivity, and, for example, readily abstract halide ligands from halocarbon solvents, eqn. (14).…”

Section: Photoinduced Cleavage Of Metal-metal Bondsmentioning

confidence: 99%

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Organometallic photochemistry

Geoffroy¹

1983

J. Chem. Educ.

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120

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“…The 17-electron metal fragments display radical-like reactivity, and, for example, readily abstract halide ligands from halocarbon solvents, eqn. (14).…”

Section: Photoinduced Cleavage Of Metal-metal Bondsmentioning

confidence: 99%

“…convert smoothly and quantitatively into H2Re2(CO)s upon photolysis, eqn. (24)(14), reactivity, although even photosubstitution occurs with quite low quantum yields (0 > 0.05), e.g. eqn.…”

mentioning

confidence: 99%

Organometallic photochemistry

Geoffroy¹

1983

J. Chem. Educ.

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120

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“…388 Table 16 below. Two other examples (67) 321 and (68) 320 are also shown in this Scheme; the structures of (65), (66) and (68) were deduced by l H NMR, while that for (67) was determined by X-ray diffraction. 389 Compound (68) is listed in Tables 14 and 16 as a consequence of the two separate features of interest which it contains.…”

Section: Synthesis Of the Equally Important Dibromo Intermediate Is Smentioning

confidence: 99%

Technetium and Rhenium

Boag

Kaesz

1982

Comprehensive Organometallic Chemistry

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“…That this difference is very small (and probably zero within the limits of accuracy) requires that either (1) E-j at Ee or (2) A1E1e~EltRT « A%E%e~Ei!Rr and A1e"E^RT « A$e~E,/RT. Any other condition would predict a temperature dependent value for the difference such that the Arrhenius slopes in Figure 5 would not be linear.…”

Section: Appendixmentioning

confidence: 99%

Liquid crystalline solvents as mechanistic probes. 6. Dynamic quenching of pyrene fluorescence by 5.alpha.-cholestan-3.beta.-yldimethylamine in the liquid crystalline and isotropic phases of a cholesteric solvent

Anderson¹,

Craig²,

Weiss³

1981

J. Am. Chem. Soc.

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A method is described for determining the specificity of quenching of pyrene singlets by a tertiary alkylamine, 5a-cholestan-3P-yldimethylamine (CA), in a nonpolar cholesteric liquid crystalline solvent [59.5/ 15.6/24.9 (w/w/w) cholesteryl oleate/cholesteryl nonanoate/cholesteryl chloride]. It is found that the pyrene-amine orientation for quenching resembles closely the probable exciplex geometry. Activation parameters for the quenching process are phase dependent: from Stern-Volmer derived quenching rate constants at low CA concentrations, the Arrhenius activation energies and preexponential factors in the cholesteric phase are calculated to be E6 = 9.9 i= 0.2 kcal mol-' and A6 = (2.1 i= 1.3) X loi4 M-' s-'; the isotropic phase has E6 = 5.3 f 0.1 kcal mol-' and A6 = (1.8 f 0.4) X 10" M-' 8. The value of E6(cholesteric) is found to change with CA concentration, approaching E,(isotropic) at high CA. A cohesive explanation of these and other results, including the previously reported photodimerization of acenaphthylene in a different cholesteric phase, is advanced.

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Photoinduced fragmentation of dodecacarbonyltrihydrotrirhenium and dodecacarbonyltrihydrotrimanganese

Cited by 31 publications

References 10 publications

Organometallic photochemistry

Organometallic photochemistry

Technetium and Rhenium

Liquid crystalline solvents as mechanistic probes. 6. Dynamic quenching of pyrene fluorescence by 5.alpha.-cholestan-3.beta.-yldimethylamine in the liquid crystalline and isotropic phases of a cholesteric solvent

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