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Electronic Structures and Reduction Potentials of Cu(II) Complexes of [N,N′-Alkyl-bis(ethyl-2-amino-1-cyclopentenecarbothioate)] (Alkyl=Ethyl, Propyl, and Butyl)

Contreras, Ricardo R. and Suárez, Trino and Reyes, Marisela and Bellandi, Fernándo and Cancines, Pedro and Moreno, Jenny and Shahgholi, Mona and Di Bilio, Angel J. and Gray, Harry B. and Fontal, Bernardo (2004) Electronic Structures and Reduction Potentials of Cu(II) Complexes of [N,N′-Alkyl-bis(ethyl-2-amino-1-cyclopentenecarbothioate)] (Alkyl=Ethyl, Propyl, and Butyl). In: Optical Spectra and Chemical Bonding in Inorganic Compounds. Structure and Bonding. No.106. Springer Berlin Heidelberg , Berlin, Heidelberg, pp. 71-79. ISBN 9783540008538. https://resolver.caltech.edu/CaltechAUTHORS:20190829-131534243

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Abstract

Copper(II) complexes of N,N’-alkyl-bis(ethyl-2-amino-1-cyclopentenecarbodithioate) [alkyl=ethyl (L2), propyl (L3), and butyl(L4)] ligands have been synthesized and characterized. Analytical data for all three complexes show 1:1 copper-ligand stoichiometry. Well-resolved EPR spectra were recorded in toluene, benzene, and methylene chloride solutions at room temperature and in glassy toluene or toluene-methylene chloride mixtures in the range 20–150 K. The superhyperfine pattern unambiguously demonstrates coordination of two nitrogen atoms to copper; and the spin-Hamiltonian parameters [CuL2, g_∥=2.115, A_∥=187×10^(–4) cm^(–1); CuL3, g_∥=2.128, A_∥=165×10^(–4) cm^(–1); CuL4, g_∥=2.138, A_∥=147×10^(–4) cm^(–1)] are as expected for a CuN_2S_2 coordination core. Quasi-reversible electrochemical behavior was observed in methylene chloride: the Cu(II)/Cu(I) reduction potentials increase from –1.17 V (E° vs Ag/AgNO_3) for CuL2 to –0.74 V for CuL4, indicating greater stabilization of Cu(I) in CuL4. Taken together, these data demonstrate that lengthening the N,N′-alkyl chain distorts the planar CuN_2S_2 core (CuL2) toward a flattened tetrahedral geometry (CuL4).


Item Type:Book Section
Related URLs:
URLURL TypeDescription
https://doi.org/10.1007/b11306DOIArticle
ORCID:
AuthorORCID
Gray, Harry B.0000-0002-7937-7876
Additional Information:© Springer-Verlag Berlin Heidelberg 2004. This work was supported by CDCHT-ULA (C-1108–01-A), the NSF, NIH, and the Arnold and Mabel Beckman Foundation.
Funders:
Funding AgencyGrant Number
Consejo de Desarrollo Científico, Humanístico, Tecnológico y de las ArtesC-1108–01-A
NSFUNSPECIFIED
NIHUNSPECIFIED
Arnold and Mabel Beckman FoundationUNSPECIFIED
Subject Keywords:Copper complexes; Reduction potentials; Electronic structures; EPR spectra
Series Name:Structure and Bonding
Issue or Number:106
Record Number:CaltechAUTHORS:20190829-131534243
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20190829-131534243
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:98353
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:30 Aug 2019 14:32
Last Modified:03 Oct 2019 21:40

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