Photodriven Elimination of Chlorine From Germanium and Platinum in a Dinuclear PtII→GeIV Complex

Karimi, Mohammadjavad; Tabei, Elham S.; Fayad, Remi; Saber, Mohamed R.; Danilov, Evgeny O.; Jones, Cameron; Castellano, Felix N.; Gabbaï, François P.

doi:10.1002/anie.202107485

Photodriven Elimination of Chlorine From Germanium and Platinum in a Dinuclear Pt^II→Ge^IV Complex

Journal Article · Mon Aug 16 00:00:00 UTC 2021 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202107485· OSTI ID:1976268

Karimi, Mohammadjavad ^[1]; Tabei, Elham S. ^[2]; Fayad, Remi ^[3]; Saber, Mohamed R. ^[2]; Danilov, Evgeny O. ^[3]; ^[4]; ^[3]; ^[2]

Texas A & M University, College Station, TX (United States); OSTI
Texas A & M University, College Station, TX (United States)
North Carolina State University, Raleigh, NC (United States)
Monash University, Melbourne, VIC (Australia)

Searching for a connection between the two-electron redox behavior of Group-14 elements and their possible use as platforms for the photoreductive elimination of chlorine, we have studied the photochemistry of [(o-(Ph₂P)C₆H₄)₂Ge^IVCl₂]Pt^IICl₂ and [(o-(Ph₂P)C₆H₄)₂ClGe^III]Pt^IIICl₃, two newly isolated isomeric complexes. These studies show that, in the presence of a chlorine trap, both isomers convert cleanly into the platinum germyl complex [(o-(Ph₂P)C₆H₄)₂ClGe^III]Pt^ICl with quantum yields of 1.7 % and 3.2 % for the Ge^IV–Pt^II and Ge^III–Pt^III isomers, respectively. Conversion of the Ge^IV–Pt^II isomer into the platinum germyl complex is a rare example of a light-induced transition-metal/main-group-element bond-forming process. Additionally, transient-absorption-spectroscopy studies carried out on the Ge^III–Pt^III isomer point to a ligand arene–Cl. charge-transfer complex as an intermediate.

View Accepted Manuscript (DOE)

Research Organization:: Princeton University, NJ (United States); Texas A & M University, College Station, TX (United States)

Sponsoring Organization:: National Science Foundation (NSF); Texas A&M University; USDOE; USDOE Office of Science (SC); Welch Foundation

Grant/Contract Number:: SC0019370

OSTI ID:: 1976268

Alternate ID(s):: OSTI ID: 1819396

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 41 Vol. 60; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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CCDC 2087876: Experimental Crystal Structure Determination Mohammadjavad, Karimi,; S., Tabei, Elham; Remi, Fayad, https://doi.org/10.5517/ccdc.csd.cc282lvt The current record is supplemented by this dataset	dataset	January 2021
CCDC 2087877: Experimental Crystal Structure Determination Mohammadjavad, Karimi,; S., Tabei, Elham; Remi, Fayad, https://doi.org/10.5517/ccdc.csd.cc282lwv The current record is supplemented by this dataset	dataset	January 2021
CCDC 2087878: Experimental Crystal Structure Determination Mohammadjavad, Karimi,; S., Tabei, Elham; Remi, Fayad, https://doi.org/10.5517/ccdc.csd.cc282lxw The current record is supplemented by this dataset	dataset	January 2021