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Spectral studies of a Cr(PNP)-MAO system for selective ethylene trimerization catalysis: searching for the active species.


ABSTRACT: Variable temperature spectroscopic, kinetic, and chemical studies were performed on a soluble CrIIICl3(PNP) (PNP = bis(diarylphosphino)alkylamine) ethylene trimerization precatalyst to map out its methylaluminoxane (MAO) activation sequence. These studies indicate that treatment of CrIIICl3(PNP) with MAO leads to first replacement of chlorides with alkyl groups, followed by alkyl abstraction, and then reduction to lower-valent species. Reactivity studies demonstrate that the majority of the chromium species detected is not catalytically active.

SUBMITTER: Do LH 

PROVIDER: S-EPMC3855459 | biostudies-literature | 2013 Nov

REPOSITORIES: biostudies-literature

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Spectral studies of a Cr(PNP)-MAO system for selective ethylene trimerization catalysis: searching for the active species.

Do Loi H LH   Labinger Jay A JA   Bercaw John E JE  

ACS catalysis 20131101 11


Variable temperature spectroscopic, kinetic, and chemical studies were performed on a soluble Cr<sup>III</sup>Cl<sub>3</sub>(PNP) (PNP = bis(diarylphosphino)alkylamine) ethylene trimerization precatalyst to map out its methylaluminoxane (MAO) activation sequence. These studies indicate that treatment of Cr<sup>III</sup>Cl<sub>3</sub>(PNP) with MAO leads to first replacement of chlorides with alkyl groups, followed by alkyl abstraction, and then reduction to lower-valent species. Reactivity studi  ...[more]

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