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DOE OSTI · 3023450

Cyclometalated Platinum Compounds from Competing C–H/C–X Bond Activation Pathways

Anderson, Craig M. [Bard College, Annandale-on-Hudson, NY (United States)] (ORCID:0000000158754380)·Greenberg, Matthew W. [Bard College, Annandale-on-Hudson, NY (United States)] (ORCID:0000000250813099)·LaFratta, Christopher N. [Bard College, Annandale-on-Hudson, NY (United States)] (ORCID:0000000345856278)·Dziubelski, Monika [Bard College, Annandale-on-Hudson, NY (United States)]·Aleem, Zainab [Bard College, Annandale-on-Hudson, NY (United States)]·Hathaway, Benett B. [Bard College, Annandale-on-Hudson, NY (United States)]·Tanski, Joseph M. [Vassar College, Poughkeepsie, NY (United States)] (ORCID:0000000274961299)
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Abstract

X−C^N^N (X = Br, Cl) ligands were reacted with [Pt 2 Me 4 (μ- SMe 2 ) 2 ], 1, resulting in a six-coordinate cyclometalated platinum(IV) compound containing an anionic C^N^N ligand when X = Br and both a platinum(IV) and a platinum(II) product when X = Cl. The platinum(II) species was formed by C−H activation, followed by reductive elimination of methane. The platinum compounds were characterized by multinuclear NMR spectroscopy and single-crystal X-ray diffraction (SCXRD). Photophysical properties were explored by using UV/vis, emission, and transient absorption (TA) spectroscopies. DFT and TDDFT calculations were performed to examine the competition between C−H activation and C−X oxidative addition and compared to experimental results.

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Anderson, Craig M. [Bard College, Annandale-on-Hudson, NY (United States)] (ORCID:0000000158754380), Greenberg, Matthew W. [Bard College, Annandale-on-Hudson, NY (United States)] (ORCID:0000000250813099), LaFratta, Christopher N. [Bard College, Annandale-on-Hudson, NY (United States)] (ORCID:0000000345856278), Dziubelski, Monika [Bard College, Annandale-on-Hudson, NY (United States)], Aleem, Zainab [Bard College, Annandale-on-Hudson, NY (United States)], Hathaway, Benett B. [Bard College, Annandale-on-Hudson, NY (United States)], Tanski, Joseph M. [Vassar College, Poughkeepsie, NY (United States)] (ORCID:0000000274961299). 2026-03-03. Cyclometalated Platinum Compounds from Competing C–H/C–X Bond Activation Pathways. https://doi.org/10.1021/acsomega.5c12884

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