Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 24, Issue 21, Pages 5513-5521Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201705957
Keywords
azides; olefin ligands; redox chemistry; ruthenium; synthetic methods
Categories
Funding
- Schweizer Nationalfonds (SNF)
- Eidgenossische Technische Hochschule Zurich
- Netherlands Organization for Scientific Research NWO-CW [016.122.613]
- FOM-NWO-Shell Computational Sciences for Energy Research Initiative [13CSER003]
- RPA Sustainable Chemistry of the University of Amsterdam
Ask authors/readers for more resources
Coordination of the diazadiene diolefin ligand (trop(2)dad) to ruthenium leads to various complexes of composition [Ru(trop(2)dad)(L)]. DFT studies indicate that the closed-shell singlet (CSS), open-shell singlet (OSS), and triplet electronic structures of this species are close in energy, with the OSS spin configuration being the lowest in energy for all tested functionals. Singlet-state CASSCF calculations revealed a significant multireference character for these complexes. The closed-shell singlet wavefunction dominates, but these complexes have a significant (approximate to 8-16%) open-shell singlet [d(7)-Ru-I(L)(trop(2)dad(center dot-))] contribution mixed into the ground state. In agreement with their ambivalent electronic structure, these complexes reveal both metal- and ligand-centered reactivity. Most notable are the reactions with AdN(3), diazomethane, and a phosphaalkyne leading to scission of the C-C bond of the diazadiene (dad) moiety of the trop(2)dad ligand, resulting in net (formal) nitrene, carbene, or P C insertion in the dad C-C bond, respectively. Supporting DFT studies revealed that several of the ligand-based reactions proceed via low-barrier radical-type pathways, involving the dad(center dot-) ligand radical character of the OSS or triplet species.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available