Minimalistic Ditopic Ligands: An α‐S, N‐Donor‐Substituted Alkyne as Effective Intermetallic Conjugation Linker. Issue 32 (30th June 2016)

• Record Type: Journal Article
• Authors: Rüger, Julia; Timmermann, Christopher; Villinger, Alexander; Hinz, Alexander; Hollmann, Dirk; Seidel, Wolfram W.
• Is Part Of: Chemistry. Volume 22:Issue 32(2016)
• Page Start: 11191
• Page End: 11195
• Publication Date: 2016-06-30
• Subjects: alkynes -- heterometallic complexes -- ligand design -- metal–metal interactions -- template synthesis; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201601403
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The capability of donor‐substituted alkynes to link different metal ions in a side‐on carbon donor‐chelate coordination mode is extended from the donor centers S and P to the second period element N. The complex [Tp′W(CO)2 {η 2 ‐C2 (S)(NHBn)}] (Tp′=hydrido‐tris(3, 5‐dimethylpyrazolyl)borate, Bn=benzyl) bearing a terminal sulfur atom and a secondary amine substituent is accessible by a metal‐template synthesis. Subsequent deprotonation allowed the formation of remarkably stable heterobimetallic complexes with the [(η 5 ‐C5 H5 )Ru(PPh3 )] and the [Ir(ppy)2 ] moiety. Electrochemical and spectroscopic investigations (cyclic voltammetry, IR, UV/Vis, luminescence, EPR), as well as DFT calculations, and X‐ray structure determinations of the W–Ru complex in two oxidation states reveal a strong metal–metal coupling but also a limited delocalization of excited states. Abstract : Less is more : The introduction of an amide group into a coordinated alkyne opens up the field of polynuclear complexes with heterodonor‐substituted alkynes. The presented investigations allow a deeper understanding of the metal–metal coupling in such unusual coordination assemblies.