Triplet energy transfer insight in coordination of unsaturated hydrocarbons by d(0) bent metallocenes (Zr, Hf).

Triplet energy transfer insight in coordination of unsaturated hydrocarbons by d(0) bent metallocenes (Zr, Hf). Research Abstract Details 

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Triplet energy transfer insight in coordination of unsaturated hydrocarbons by d(0) bent metallocenes (Zr, Hf). Abstract Text:

Galina V Loukova,Svetlana E Starodubova,Vyatcheslav A Smirnov,Galina V Loukova,Svetlana E Starodubova,Vyatcheslav A Smirnov,

For a class of pi-complexes as energy donors, with the use of highly emissive d(0) metallocenes Cp(2)MCl(2) where M = Zr and Hf, it is shown that radiationless triplet energy transfer to unsaturated hydrocarbons in a rigid nonpolar methylcyclohexane (MCH) matrix (where molecular diffusion is absent) obeys the Perrin equation, occurs at radii R(0), being close to the diameter of interacting molecules, and is well described by an electron-exchange resonant (Dexter) mechanism of interaction. Principle correlation between values of the critical radius and a number of C atoms in a linear alpha-olefin is for the first time reported, viz. R(0) (Angstrom) = -2.47 + 1.35n (obtained for systems [Cp(2)HfCl(2) + CnH(2)n + MCH] at 77 K). Pronounced blue shifts (up to 1000 cm(-1)) of low-temperature emission spectra of Cp(2)ZrCl(2) in MCH in the presence of dienes, possessing nonconjugated C=C bonds, are observed, thus suggesting inner-sphere diene coordination. In view of the experimental data, inner- and outer-sphere coordinative interaction between the components of catalytic systems for polymerization (d(0) metallocene precatalysts and alkenes and dienes) is rationalized.

Triplet energy transfer insight in coordination of unsaturated hydrocarbons by d(0) bent metallocenes (Zr, Hf). Publishing Authors By Initials

GV Loukova,SE Starodubova,VA Smirnov,GV Loukova,SE Starodubova,VA Smirnov,

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Triplet energy transfer insight in coordination of unsaturated hydrocarbons by d(0) bent metallocenes (Zr, Hf). Journal Published:

PUBLICATION TYPE: Journal Article

Journal: The journal of physical chemistry. A

VOLUME: 111

Page Numbers: 10928-37

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ISSN: 1089-5639

DAY: 11

MONTH: 10

YEAR: 2007

Triplet energy transfer insight in coordination of unsaturated hydrocarbons by d(0) bent metallocenes (Zr, Hf). Information

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LANGUAGE: eng

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Grant and Affiliation Information for Triplet energy transfer insight in coordination of unsaturated hydrocarbons by d(0) bent metallocenes (Zr, Hf).

AFFILIATION: Institute of Problems of Chemical Physics, Russian Academy of Sciences, 142432 Chernogolovka, Moscow Region, Russia. gloukova@cat.icp.ac.ru

Country: United States

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MEDLINETA: J Phys Chem A

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