Identification of Reactive Intermediates Relevant to Dimethylgermylene Group Transfer Reactions of an Anthracene-Based Precursor
Author(s)
Geeson, Michael Baily; Transue, Wesley; Cummins, Christopher C
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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.
Date issued
2019-08Department
Massachusetts Institute of Technology. Department of ChemistryJournal
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
ISSN
0276-7333
1520-6041