Issue 7, 2016

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

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 [(CuII(L-N2S2))42-CuI(MeCN)2)23-CuI(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 [CuII(L-N2S2] centers held in distorted four-coordinate environments and joined by μ2-CuI(MeCN)23-CuI(MeCN) ions that bridge their thiolate sulfur atoms. Each four-coordinate [CuII(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+.

Graphical abstract: An S4-symmetric mixed-valent decacopper cage comprised of [CuII(L-S2N2)] complexes bridged by CuI(MeCN)n (n = 1 or 2) cations

Supplementary files

Article information

Article type
Paper
Submitted
05 Nov 2015
Accepted
05 Jan 2016
First published
05 Jan 2016

Dalton Trans., 2016,45, 2997-3002

Author version available

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

S. J. Ferrara, B. Wang and J. P. Donahue, Dalton Trans., 2016, 45, 2997 DOI: 10.1039/C5DT04359J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements