CaltechAUTHORS
  A Caltech Library Service

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. https://resolver.caltech.edu/CaltechAUTHORS:20180529-112353490

[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
See Usage Policy.

784Kb

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20180529-112353490

Abstract

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/ic961146vDOIArticle
https://pubs.acs.org/doi/suppl/10.1021/ic961146vPublisherSupporting Information
ORCID:
AuthorORCID
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.
Funders:
Funding AgencyGrant Number
Alexander von Humboldt FoundationUNSPECIFIED
NSFUNSPECIFIED
Arnold and Mabel Beckman FoundationUNSPECIFIED
Redox Pharmaceutical CorporationUNSPECIFIED
Issue or Number:12
Record Number:CaltechAUTHORS:20180529-112353490
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180529-112353490
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
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:29 May 2018 19:41
Last Modified:22 Nov 2019 09:58

Repository Staff Only: item control page