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Metal-Metal Cooperative Bond Activation by Heterobimetallic Alkyl, Aryl, and Acetylide PtII/CuI Complexes

preprint
submitted on 28.01.2020 and posted on 29.01.2020 by Shubham Deolka, Orestes Rivada Wheelaghan, Sandra Aristizábal, Robert Fayzullin, Shrinwantu Pal, Kyoko Nozaki, Eugene Khaskin, Julia Khusnutdinova
We report selective formation of heterobimetallic PtII/CuI complexes that demonstrate how facile bond activation processes can be achieved by altering reactivity of common organoplatinum compounds through their interaction with another metal center. The interaction of the Cu center with Pt center and with a Pt-bound alkyl group increases the stability of PtMe2 towards undesired rollover cyclometalation. The presence of the CuI center also enables facile transmetalation from electron-deficient tetraarylborate [B(ArF)4]- anion and mild C-H bond cleavage of a terminal alkyne, which was not observed in the absence of an electrophilic Cu center. The DFT study indicates that the role of Cu center acts as a binding site for alkyne substrate, while activating its terminal C-H bond.

Funding

JSPS Kakenhi Grant Number 16F16038

History

Email Address of Submitting Author

juliak@oist.jp

Institution

Okinawa Institute of Science and Technology Graduate University

Country

Japan

ORCID For Submitting Author

0000-0002-5911-4382

Declaration of Conflict of Interest

The authors declare no conflict of interests.

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