Identification of Reactive Intermediates Relevant to Dimethylgermylene Group Transfer Reactions of an Anthracene-Based Precursor
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acs.organomet.9b00410.pdf
Description
Published version
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769.92 KB
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Adobe PDF
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Author(s)
Geeson, Michael Baily
Transue, Wesley
Cummins, Christopher C
Date Issued
August 2019
Journal
Organometallics
Publisher
American Chemical Society (ACS)
Citation
Geeson, Michael B. et al. "Identification of Reactive Intermediates Relevant to Dimethylgermylene Group Transfer Reactions of an Anthracene-Based Precursor." Organometallics 38, 17 (August 2019): 3229-3232 © 2019 American Chemical Society
Version
Final published version
Abstract
Dimethylgermylene ([Me₂Ge]) group transfer from the anthracene-based precursor dibenzo-7-dimethylgermanorbornadiene (Me₂GeA; A = C₁₄H₁₀, anthracene) was investigated. Transfer of [Me₂Ge] from Me₂GeA to 2,3-dimethylbutadiene to give a dihydrogermole (2) was mediated by a platinum metallagermacycle (1), formed by oxidative addition of the platinum(0) species (Ph₃P)₂Pt(C₂H₄) into the strained Ge-C bond of Me₂GeA with concomitant loss of ethylene. Metallagermacycle 1 was characterized by multinuclear NMR spectroscopy, single-crystal X-ray diffraction, and elemental analysis. The strained Ge-C bond of Me₂GeA was also found to undergo an addition reaction with pyridine, resulting in the [2.2.3]-bicyclic compound 3. Kinetics experiments on both the platinum- and pyridine-promoted systems implicate low-valent dimethylgermylene-containing species as reaction intermediates.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Creative Commons Attribution-NonCommercial-NoDerivs License
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DOI of Published Version
https://doi.org/10.1021/acs.organomet.9b00410
