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Spectroscopy and Electrochemistry of Cobalt(III) Schiff Base Complexes

Böttcher, Arnd and Takeuchi, Toshihiko and Hardcastle, Kenneth I. and Meade, Thomas J. and Gray, Harry B. and Cwikel, Dory and Kapon, Moshe and Dori, Zvi (1997) Spectroscopy and Electrochemistry of Cobalt(III) Schiff Base Complexes. Inorganic Chemistry, 36 (12). pp. 2498-2504. ISSN 0020-1669. doi:10.1021/ic961146v.

[img] PDF (Text describing X-ray procedures and tables of X-ray crystallographic data (atomic coordinates, bond distances and angles, anisotropic displacement parameters, hydrogen coordinates) for [Co(3-Cl-acacen)(NH3)2]BPh4 and [Co(acacen)(4-MeIm)2]Br·1.5H2O (21 pa) - Supplemental Material
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The structural, spectroscopic, and electrochemical properties of cobalt(III) derivatives of acacen (H_2acacen = bis(acetylacetone) ethylenediimine) and related ligands have been investigated. Electronic structure calculations indicate that the absorption between 340 and 378 nm in Co^(III)(acacen) spectra is attributable to the lowest π−π* intraligand charge-transfer transition. Equatorial ligand substitutions affect reduction potentials less than axial ligand changes, consistent with an electronic structural model in which d_(z^2) is populated in forming cobalt(II). The crystal structure of [Co(3-Cl-acacen)(NH_3)_2]BPh_4 has been determined:  The compound crystallizes in the monoclinic space group (P2_1)/m (No. 11) with a = 9.720(2) Å, b = 18.142(4) Å, c = 10.046(2) Å, β = 100.11(3)°, D_c = 1.339 g cm^(-3), and Z = 2; the complex cation, [Co(3-Cl-acacen)(NH_3)_2]^+, exhibits a slightly distorted octahedral coordination geometry. The distances between the cobalt atom and the two axial nitrogen donor atoms differ only slightly (1.960(6) and 1.951(6) Å) and are similar to Co−N distances found in cobalt−ammine complexes as well as the axial Co−N distances in [Co(acacen)(4-MeIm)_2]Br·1.5H_2O; the latter compound crystallizes in the triclinic space group P1̄ (No. 2) with a = 18.466(9) Å, b = 14.936(7) Å, c = 10.111(5)Å, α = 96.27(5)°, β = 94.12(5)°, γ = 112.78(5)°, D_c = 1.447 g cm^(-3), and Z = 4.

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Gray, Harry B.0000-0002-7937-7876
Additional Information:© 1997 American Chemical Society. Received September 18, 1996. A.B. thanks the Alexander von Humboldt Foundation for a postdoctoral fellowship. This work was supported by NSF, the Arnold and Mabel Beckman Foundation, and Redox Pharmaceutical Corp.
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Alexander von Humboldt FoundationUNSPECIFIED
Arnold and Mabel Beckman FoundationUNSPECIFIED
Redox Pharmaceutical CorporationUNSPECIFIED
Issue or Number:12
Record Number:CaltechAUTHORS:20180529-112353490
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Official Citation:Spectroscopy and Electrochemistry of Cobalt(III) Schiff Base Complexes Arnd Böttcher, Toshihiko Takeuchi, Kenneth I. Hardcastle, Thomas J. Meade, Harry B. Gray Dory Cwikel, Moshe Kapon, and Zvi Dori Inorganic Chemistry 1997 36 (12), 2498-2504 DOI: 10.1021/ic961146v
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86665
Deposited By: George Porter
Deposited On:29 May 2018 19:41
Last Modified:15 Nov 2021 20:40

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