An S4-symmetric mixed-valent decacopper cage comprised of [Cu(II)(L-S2N2)] complexes bridged by Cu(I)(MeCN)n (n = 1 or 2) cations.


Journal article


S. Ferrara, Bo Wang, J. P. Donahue
Dalton transactions, 2016

Semantic Scholar DOI PubMed
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APA   Click to copy
Ferrara, S., Wang, B., & Donahue, J. P. (2016). An S4-symmetric mixed-valent decacopper cage comprised of [Cu(II)(L-S2N2)] complexes bridged by Cu(I)(MeCN)n (n = 1 or 2) cations. Dalton Transactions.


Chicago/Turabian   Click to copy
Ferrara, S., Bo Wang, and J. P. Donahue. “An S4-Symmetric Mixed-Valent Decacopper Cage Comprised of [Cu(II)(L-S2N2)] Complexes Bridged by Cu(I)(MeCN)n (n = 1 or 2) Cations.” Dalton transactions (2016).


MLA   Click to copy
Ferrara, S., et al. “An S4-Symmetric Mixed-Valent Decacopper Cage Comprised of [Cu(II)(L-S2N2)] Complexes Bridged by Cu(I)(MeCN)n (n = 1 or 2) Cations.” Dalton Transactions, 2016.


BibTeX   Click to copy

@article{s2016a,
  title = {An S4-symmetric mixed-valent decacopper cage comprised of [Cu(II)(L-S2N2)] complexes bridged by Cu(I)(MeCN)n (n = 1 or 2) cations.},
  year = {2016},
  journal = {Dalton transactions},
  author = {Ferrara, S. and Wang, Bo and Donahue, J. P.}
}

Abstract

Oxidative addition of 1,2,11,12-tetrathia-5,8,15,19-tetra(N-methylamino)cycloicosane, the bis(disulfide) form of N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)ethylenediamine (L-N2S2) to [Cu(MeCN)4][BF4] (2.5 eq.) in MeCN produces good yields of the decacopper cage compound [(Cu(II)(L-N2S2))4(μ2-Cu(I)(MeCN)2)2(μ3-Cu(I)(MeCN))4][BF4]6·2.25MeCN, [1][BF4]6·2.25MeCN. This mixed-valent hexacation shows idealized S4 point group symmetry and is composed of four [Cu(II)(L-N2S2] centers held in distorted four-coordinate environments and joined by μ2-Cu(I)(MeCN)2/μ3-Cu(I)(MeCN) ions that bridge their thiolate sulfur atoms. Each four-coordinate [Cu(II)(L-N2S2)] center is related to the other three by successive executions of the S4 operation. A dark violet color is observed for [1](6+) and attributed to a combination of metal-to-ligand (S), ligand (S)-to-metal, and, at lower energy, intermetal charge transfer transitions, as found for Cu5 cage compounds with a compositional relationship to [1](6+).


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