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, Diran; Bothe, Eberhard; Neese, Frank; Weyhermüller, Thomas; Wieghardt, Karl

doi:10.1021/ja030123u

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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

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Herebian, Diran
Research Department Wieghardt, Max Planck Institute for Radiation Chemistry, Max Planck Society;

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Bothe, Eberhard
Research Department Wieghardt, Max Planck Institute for Radiation Chemistry, Max Planck Society;

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Neese, Frank
Research Department Wieghardt, Max Planck Institute for Radiation Chemistry, Max Planck Society;

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Weyhermüller, Thomas
Research Department Wieghardt, Max Planck Institute for Radiation Chemistry, Max Planck Society;

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

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Citation

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.

Cite as: https://hdl.handle.net/21.11116/0000-0008-10BF-F

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: [M^II(²L^ISQ)₂], M = Ni (1), Pd (2), Pt (3), and [M^II(³L^ISQ)₂] M = Ni (4), Pd (5), Pt (6). H₂[²L^PDI] represents 3,5-di-tert-butyl-o-phenylenediamine and H₂[³L^PDI] is N-phenyl-o-phenylenediamine; (L^ISQ)^1- is the o-diiminobenzosemiquinonate π radical anion, and (L^IBQ)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 [M^II(L^ISQ)(L^IBQ)]⁺ and [M^II(L^ISQ)(L^PDI)]^-, respectively. One-electron oxidations of 1 and trans-6 yield the diamagnetic dications {cis-[Ni^II(²L^ISQ)(²L^IBQ)]₂}Cl₂ (7) and {trans-[Pt^II(³L^ISQ)(³L^IBQ)]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.