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Minimalistic Ditopic Ligands: An α‐S,N‐Donor‐Substituted Alkyne as Effective Intermetallic Conjugation Linker
Author(s) -
Rüger Julia,
Timmermann Christopher,
Villinger Alexander,
Hinz Alexander,
Hollmann Dirk,
Seidel Wolfram W.
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201601403
Subject(s) - deprotonation , chemistry , alkyne , moiety , delocalized electron , substituent , electron paramagnetic resonance , photochemistry , amine gas treating , metal , linker , medicinal chemistry , crystallography , stereochemistry , ion , organic chemistry , catalysis , physics , nuclear magnetic resonance , computer science , operating system
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 ‐C 2 (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 ‐C 5 H 5 )Ru(PPh 3 )] 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.