Minimalistic Ditopic Ligands: An α-S,N-Donor-Substituted Alkyne as Effective Intermetallic Conjugation Linker.
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.
Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059, Rostock, Germany.
Julia
J
Rüger
Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059, Rostock, Germany.
Christopher
C
Timmermann
Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059, Rostock, Germany.
Alexander
A
Villinger
Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059, Rostock, Germany.
Alexander
A
Hinz
Leibniz-Institut für Katalyse e.V., Albert-Einstein-Str. 29a, 18059, Rostock, Germany.
Dirk
D
Hollmann
Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059, Rostock, Germany. wolfram.seidel@uni-rostock.de.
Wolfram W
http://orcid.org/0000-0003-1891-361X
WW
Seidel
alkynes; heterometallic complexes; ligand design; metal-metal interactions; template synthesis