Phosphorescent Thiazol-2-ylidene Platinum(II) Complexes with β-Ketoiminates: Single Isomer Formation by Ligand Architecture

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• 作者：Hendrik Leopold ; Thomas Strassner
• 刊名：Organometallics
• 出版年：2016
• 出版时间：December 27, 2016
• 年：2016
• 卷：35
• 期：24
• 页码：4050-4059
• 全文大小：561K
• ISSN：1520-6041

文摘

We present the synthesis and photophysical properties of six novel N-phenyl-1,3-thiazol-2-ylidene platinum(II) complexes with sterically demanding N-aryl-β-ketoiminate ligands. Diverse aryl substituents at the coordinating nitrogen atom (phenyl, mesityl, 2,6-diisopropylphenyl, 4-cyanophenyl, 1-naphthyl, and 2,4-difluorophenyl) of the N-aryl-(3Z)-4-amino-3-penten-2-ones exclusively yielded the SP-4-3 coordinated C^∧C* cyclometalated platinum(II) complexes as single isomers as a consequence of the low steric demand of the C^∧C* cyclometalating thiazole ligand and the bulkiness of the β-ketoiminate ligands. The formation of this isomer was confirmed by ¹⁹⁵Pt NMR and extensive 2D NMR experiments, two solid-state structures, and the results of DFT calculations. As a proof of principle, two complexes with the sterically less demanding β-ketoiminate ligands (3Z)-4-amino-3-penten-2-onato and (2Z)-3-amino-1-phenyl-2-buten-1-onato were synthesized and isolated as an isomeric mixture.