Cyclometalated Ni(II) Complexes [Ni((NCN)-C-boolean AND-N-boolean AND)X] of the Tridentate 2,6-di(2-pyridyl)phen-ide Ligand

A series of cyclometalated Ni(II) complexes [Ni(PyPhPy)X] containing anionic (NCN-)-C-boolean AND-N-boolean AND tridentate ligand Py(Ph-)Py 2,6-di(2-pyridyl)benzene1-ide, (Py(HPh)Py = 1,3-di(2-pyridyl)benzene) and X = Cl, Br, or I as coligands, were studied. All three complexes were obtained through...

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Bibliographic Details
Published in:Organometallics Vol. 39; no. 15; pp. 2820 - 2829
Main Authors: Kletsch, Lukas, Hoerner, Gerald, Klein, Axel
Format: Journal Article
Language:English
Published: WASHINGTON Amer Chemical Soc 10.08.2020
Subjects:
Chemistry
Chemistry, Inorganic & Nuclear
Chemistry, Organic
Physical Sciences
Science & Technology
NICKEL-COMPLEXES
CARBENE
PLATINUM(II) COMPLEXES
MOLECULAR-STRUCTURE
6-PHENYL-2,2-BIPYRIDINE
REACTIVITY
CRYSTAL-STRUCTURES
BOND ACTIVATION
HYDROHETEROARYLATION
METAL-COMPLEXES
ISSN:0276-7333, 1520-6041
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Summary:A series of cyclometalated Ni(II) complexes [Ni(PyPhPy)X] containing anionic (NCN-)-C-boolean AND-N-boolean AND tridentate ligand Py(Ph-)Py 2,6-di(2-pyridyl)benzene1-ide, (Py(HPh)Py = 1,3-di(2-pyridyl)benzene) and X = Cl, Br, or I as coligands, were studied. All three complexes were obtained through direct C-H base-assisted nickelation from NiX2 and Py(HPh)Py using KOAc/K2CO3 in nonpolar high-boiling point solvents. While the overall molecular structures are quite similar to those of the previously studied [Ni((CNN)-N-boolean AND-N-boolean AND)X] complexes with the anionic (CNN)-N-boolean AND-N-boolean AND tridentate -Phbpy (HPhbpy = 6-(phenyl)-2,2'-bipyridine) ligand, bond lengths in the molecular structures are slightly different. Large differences between these (NCN)-C-boolean AND-N-boolean AND and (CNN)-N-boolean AND-N-boolean AND Ni complexes which can be traced to the different orientation of the X coligand to the carbanionic phen-ide group, trans or cis, and the different ligand pattern, Py-Ph-Py versus Ph-Py-Py, were found for the UV-vis absorption spectra and the electrochemical reductions, while the oxidation potentials are very similar. Extended DFT calculations with the TPSSh functional associate the indifference of oxidation potentials with conserved energies of metal-borne HOMOs. By contrast, the diminished pi-acceptor qualities of the (NCN)-C-boolean AND-N-boolean AND ligand translate into a destabilization of the LUMO by ca. 400 mV and a blue-shift of the leading visible transition by 80 nm in very good agreement with the experimental data.
ISSN:0276-7333
1520-6041
DOI:10.1021/acs.organomet.0c00355