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C–P vs C–H Bond Cleavage of Triphenylphosphine at Platinum(0) : Mechanism of Formation, Reactivity, Redox Chemistry, and NMR Chemical Shift Calculations of a μ-Phosphanido Diplatinum(II) Platform

Title data

Berkefeld, Andreas ; Reimann, Marc ; Hörner, Gerald ; Kaupp, Martin ; Schubert, Hartmut:
C–P vs C–H Bond Cleavage of Triphenylphosphine at Platinum(0) : Mechanism of Formation, Reactivity, Redox Chemistry, and NMR Chemical Shift Calculations of a μ-Phosphanido Diplatinum(II) Platform.
In: Organometallics. Vol. 39 (2020) Issue 3 . - pp. 443-452.
ISSN 1520-6041
DOI: https://doi.org/10.1021/acs.organomet.9b00807

Project information

Project financing: Deutsche Forschungsgemeinschaft

Abstract in another language

Transition-metal phosphanides M–PR2 are key intermediates in catalytic C–P bond functionalization. M–PR2 formation from tertiary phosphines through P–C bond cleavage widens the scope beyond P–H functionalized substrates, but mechanistic understanding of this reaction still is fragmentary. Starting from a defined coordination complex has allowed monitoring the reaction of a Pt-PPh3 moiety and Pt(0) by NMR spectroscopy. Initial Pt(0) transfer is rate-limiting and leads to products from PPh3-borne ortho-C–H and C–P bond cleavage along kinetically distinct pathways. Albeit kinetically favored, the reversibility of C–H bond cleavage eventually leads to thermodynamically preferred C–P bond scission. This pathway affords a robust [Pt(μ-PPh2)Pt] core structure whose redox chemistry and reactivity toward external ligands are reported. Organometallic products have been substantiated by a combination of magnetic resonance and absorption spectroscopies, X-ray diffraction, and DFT computations.

Further data

Item Type: Article in a journal
Refereed: Yes
Institutions of the University: Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Inorganic Chemistry IV
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Inorganic Chemistry IV > Chair Inorganic Chemistry IV - Univ.-Prof. Dr. Birgit Weber
Result of work at the UBT: Yes
DDC Subjects: 500 Science > 540 Chemistry
Date Deposited: 26 Jun 2020 07:06
Last Modified: 26 Jun 2020 07:06
URI: https://eref.uni-bayreuth.de/id/eprint/55626