Novel Sulfonated CNN Pincer Ligands for Facile C−H Activation at a Pt(II) Center

Journal Article · Fri Oct 06 00:00:00 EDT 2017 · Israel Journal of Chemistry

DOI:https://doi.org/10.1002/ijch.201700063· OSTI ID:1398284

Watts, David ^[1]; Wang, Daoyong ^[1]; Zavalij, Peter Y. ^[1]; Vedernikov, Andrei N. ^[1]

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1. Department of Chemistry and Biochemistry University of Maryland College Park MD 20742

Abstract

Two novel sulfonated CNN‐pincer ligands 1b and 1c and the corresponding chloro and aqua complexes K[ ^CNN LPtCl] and ^CNN LPt(H ₂ O), 3b – 3c and 2b – 2c , were prepared and fully characterized including single crystal X‐ray diffraction. Along with the previously described complexes 2a and 3a , the derivatives of a CNN pincer ligand 1a , these complexes form a family of structurally similar compounds where the pincer core rigidity increases in the series 2a (3a) < 2b (3b) < 2c ( 3c ), as deduced from their XRD data. The increased ligand rigidity affects the aqua ligand dissociation energy of the ^CNN LPt(H ₂ O) complexes, as it follows from DFT calculations and as is reflected in the increased reactivity of the aqua complexes 2a , 2b and 2c in processes that involve aqua ligand loss. Among these processes the formation of the presumed dinuclear complexes ^CNN L ₂ Pt ₂ and, importantly, catalytic C−D bond cleavage in C ₆ D ₆ were studied in 2,2,2‐trifluoroethanol solutions. The C−D bond cleavage reactivity was quantified as the rate of H/D exchange between C ₆ D ₆ and CF ₃ CH ₂ OH at 80 °C.

• Sponsoring Organization: USDOE
• Grant/Contract Number: NONE; SC0001298
• OSTI ID: 1398284
• Alternate ID(s): OSTI ID: 1537571
• Journal Information: Israel Journal of Chemistry, Journal Name: Israel Journal of Chemistry Journal Issue: 10-11 Vol. 57; ISSN 0021-2148
• Publisher: Wiley Blackwell (John Wiley & Sons)
• Country of Publication: Israel
• Language: English