Coordination Modes, Oxidation, and Protonation Levels of 2,6-Pyridinediimine 
and 2,2 ':6 ',2 '-Terpyridine Ligands in New Complexes of Cobalt, Zirconium, 
and Ruthenium. An Experimental and Density Functional Theory Computational Study

Wang, Mei; Römelt, Christina; Weyhermüller, Thomas; Wieghardt, Karl Ernst

doi:10.1021/acs.inorgchem.8b01949

Item

ITEM ACTIONSEXPORT

Add to Basket

Local TagsRelease HistoryDetailsSummary

Released

Journal Article

Coordination Modes, Oxidation, and Protonation Levels of 2,6-Pyridinediimine and 2,2 ':6 ',2 '-Terpyridine Ligands in New Complexes of Cobalt, Zirconium, and Ruthenium. An Experimental and Density Functional Theory Computational Study

MPS-Authors

/persons/resource/persons237848

Römelt, Christina
Research Department Schlögl, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

/persons/resource/persons237747

Weyhermüller, Thomas
Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

/persons/resource/persons237748

Wieghardt, Karl Ernst
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

External Resource

No external resources are shared

Fulltext (restricted access)

There are currently no full texts shared for your IP range.

Fulltext (public)

There are no public fulltexts stored in PuRe

Supplementary Material (public)

There is no public supplementary material available

Citation

Wang, M., Römelt, C., Weyhermüller, T., & Wieghardt, K. E. (2019). Coordination Modes, Oxidation, and Protonation Levels of 2,6-Pyridinediimine and 2,2 ':6 ',2 '-Terpyridine Ligands in New Complexes of Cobalt, Zirconium, and Ruthenium. An Experimental and Density Functional Theory Computational Study. Inorganic Chemistry, 58(1), 121-132. doi:10.1021/acs.inorgchem.8b01949.

Cite as: https://hdl.handle.net/21.11116/0000-0006-78B6-6

Abstract

The syntheses and molecular and electronic structures of the following complexes have been established by single crystal X-ray crystallography and UV-vis-NIR spectroscopy, and verified by density functional theory calculations (DFT B3LYP): [(eta(5)-Cp)(2)Zr-IV(tpy(2-))](0) (S = 0) 1, [(eta(5)-Cp)(2)Zr-IV-((OMe)pdi(2-))](0) (S = 0) 2, [Co-II((OMe)pdi(center dot))(eta(2)-BH4)](0) (S = 0) 4, [Ru-II((OMe)pdi-H)Cl(PPh3)(2)](0) (S = 0) 5, cis-[Ru-II((OMe)pdi(0))Cl-2(PPh3)](0) (S = 0) 6, and [Run(II)(eta(2)-(OMe)pdi(0))(eta(2)-(OMe)pdi-H)(2)](0) (S = 0) 7, with (tpy(0)) being neutral 2,2':6',2'-terpyridine, (tpy(center dot))(1-) its pi radical anion, (tpy(2-))(2-) its dianion; ((OMe)pdi(0)) neutral 2,6-bis(4-methoxyphenylmethylimine)pyridine, ((OMe)pdi(center dot))(1-) its radical anion and ((OMe)pdi(2-))(2-) its dianion; ((OMe)pdi-H)(1-) represents the deprotonated form of the ((OMe)pdi(0)) ligand where deprotonation takes place at the meta-position of the pyridine ring. Density functional theory calculations using the B3LYP functional were performed, establishing geometry optimized molecular and electronic structures. The structural parameter Delta = [(average distance C-py-C-imine) - (av. distance C-py - N-py + av. distance C-imine-N-imime)] is introduced for the characterization of the oxidation level of pdi (and analogously of tpy) ligands of M(pdi) (or M(tpy)) motifs for first row transition metals. The M(L-0) unit in second and third row low-valent transition metal ion complexes may exhibit significant pi-backdonation M -> L-0 structural effects.