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  Molecular and Electronic Structures of Bis-(o-diiminobenzosemiquinonato)metal(II) Complexes (Ni, Pd, Pt), Their Monocations and -Anions, and of Dimeric Dications Containing Weak Metal−Metal Bonds

Herebian, D., Bothe, E., Neese, F., Weyhermüller, T., & Wieghardt, K. (2003). Molecular and Electronic Structures of Bis-(o-diiminobenzosemiquinonato)metal(II) Complexes (Ni, Pd, Pt), Their Monocations and -Anions, and of Dimeric Dications Containing Weak Metal−Metal Bonds. Journal of the American Chemical Society, 125(30), 9116-9128. doi:10.1021/ja030123u.

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 Creators:
Herebian, Diran1, Author              
Bothe, Eberhard1, Author              
Neese, Frank1, Author              
Weyhermüller, Thomas1, Author              
Wieghardt, Karl1, Author              
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1Research Department Wieghardt, Max Planck Institute for Radiation Chemistry, Max Planck Society, ou_3023885              

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 Abstract: Two series of square planar, diamagnetic, neutral complexes of nickel(II), palladium(II), and platinum(II) containing two N,N-coordinated o-diiminobenzosemiquinonate(1-) π radical ligands have been synthesized and characterized by UV−vis and 1H NMR spectroscopy:  [MII(2LISQ)2], M = Ni (1), Pd (2), Pt (3), and [MII(3LISQ)2] M = Ni (4), Pd (5), Pt (6). H2[2LPDI] represents 3,5-di-tert-butyl-o-phenylenediamine and H2[3LPDI] is N-phenyl-o-phenylenediamine; (LISQ)1- is the o-diiminobenzosemiquinonate π radical anion, and (LIBQ)0 is the o-diiminobenzoquinone form of these ligands. The structures of complexes 1, 4, 5, and 6 have been (re)determined by X-ray crystallography at 100 K. Cyclic voltammetry established that the complete electron-transfer series consisting of a dianion, monoanion, neutral complex, a mono- and a dication exists:  [M(L)2]zz = −2, −1, 0, 1+, 2+. Each species has been electrochemically generated in solution and their X-band EPR and UV−vis spectra have been recorded. The oxidations and reductions are invariably ligand centered. Two o-diiminobenzoquinones(0) and two fully reduced o-diiminocatecholate(2-) ligands are present in the dication and dianion, respectively, whereas the monocations and monoanions are delocalized mixed valent class III species [MII(LISQ)(LIBQ)]+ and [MII(LISQ)(LPDI)]-, respectively. One-electron oxidations of 1 and trans-6 yield the diamagnetic dications {cis-[NiII(2LISQ)(2LIBQ)]2}Cl2 (7) and {trans-[PtII(3LISQ)(3LIBQ)]2}(CF3SO3)2 (8), respectively, which have been characterized by X-ray crystallography; both complexes possess a weak M···M bond and the ligands adopt an eclipsed configuration due to weak bonding interactions via π stacking.

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Language(s): eng - English
 Dates: 2003-02-192003-07-01
 Publication Status: Published in print
 Pages: 13
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ja030123u
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Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 125 (30) Sequence Number: - Start / End Page: 9116 - 9128 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870