TY - JOUR
AU - Donahue, James P.
AB - 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))4(μ2-CuI(MeCN)2)2(μ3-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)2/μ3-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+.
TI - An S4-symmetric mixed-valent decacopper cage comprised of [CuII(L-S2N2)] complexes bridged by CuI(MeCN)n (n = 1 or 2) cations
JF - Dalton Transactions
DO - 10.1039/c5dt04359j
DA - 2016-02-09
UR - https://www.deepdyve.com/lp/royal-society-of-chemistry/an-s4-symmetric-mixed-valent-decacopper-cage-comprised-of-cuii-l-s2n2-WWWsIg6u18
SP - 2997
EP - 3002
VL - 45
IS - 7
DP - DeepDyve
ER -