Synthesis and Characterization of Dithia[3.3]metaparacyclophane‐Bridged Dimetallic Ruthenium Acetylide Complexes. Issue 1 (2nd December 2013)

• Record Type: Journal Article
• Authors: Xia, Jianlong; Ou, Ya‐Ping; Meng, Xiang‐Gao; Yin, Jun; Yu, Guang‐ao; Liu, Sheng Hua
• Is Part Of: European journal of inorganic chemistry. Issue 1(2014)
• Page Start: 247
• Page End: 255
• Publication Date: 2013-12-02
• Subjects: Bridging ligands -- Cyclophanes -- Ruthenium -- Dimetallic complexes -- Redox chemistry -- Pi interactions; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201301304
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: Four dithia[3.3]metaparacyclophane‐bridged dimetallic ruthenium acetylide complexes (1 –4 ), in which the cyclophane units exhibit characteristic edge‐to‐face interactions between the top and bottom aromatic decks, have been designed, synthesized, and structurally characterized. X‐ray diffraction analysis of1 –3 revealed that effective edge‐to‐face interactions exist in the solid state. IR spectroelectrochemical results suggest that the dithia[3.3]metaparacyclophane bridging ligands are redox‐noninnocent. The UV/Vis/NIR spectra of1 +, 2 +, 3 +, and4 + display characteristic band envelopes, and the deconvoluted multiple transitions have been assigned with the aid of DFT calculations to combinations of metal‐to‐ligand charge transfer (MLCT) and ligand‐to‐ligand charge transfer (LLCT) with appreciable contributions from transannular π–π transitions, especially for3 + and4 + . Abstract : Four redox‐noninnocent dithia[3.3]metaparacyclophane‐bridged dimetallic ruthenium acetylide complexes1 –4 have been designed and synthesized. The radical cations and dications of complexes1 –4 are generated by in situ chemical oxidation with ferrocenium hexafluorophosphate ([FcH][PF6 ]) and characterized by IR and UV/Vis/NIR spectroscopy.