Neutral thioether and selenoether macrocyclic coordination to Group 1 cations (Li-Cs) - synthesis, spectroscopic and structural properties

Dalton Transactions : an International Journal of Inorganic Chemistry
Martin J D ChampionGillian Reid

Abstract

The complexes [M(L)][BAr(F)] (BAr(F) = tetrakis{3,5-bis(trifluoromethyl)-phenyl}borate), L = [18]aneO4S2 (1,4,10,13-tetraoxa-7,16-dithiacyclooctadecane): M = Li-Cs; L = [18]aneO2S4 (1,10-dioxa-4,7,13,16-tetrathiacyclooctadecane): M = Li, Na, K; L = [18]aneO4Se2 (1,4,10,13-tetraoxa-7,16-diselenacyclooctadecane): M = Na, K, as well as [Na(18-crown-6)][BAr(F)], are obtained in good yield as crystalline solids by reaction of M[BAr(F)] with the appropriate macrocycle in dry CH2Cl2. X-ray crystallographic analyses of [Li([18]aneO4S2)][BAr(F)] and [Li([18]aneO2S4)][BAr(F)] show discrete distorted octahedral cations with hexadentate coordination to the macrocycle. The heavier alkali metal complexes all contain hexadentate coordination of the heterocrown, supplemented by MF interactions via the anions, producing extended structures with higher coordination numbers; Na: CN = 7 or 8; K: CN = 8; Rb: CN = 9; Cs: CN = 8 or 10. Notably, all of the structures exhibit significant M-S/Se coordination. The crystal structures of the potassium and rubidium complexes show two distinct [M(heterocrown)](+) cations, one with MF interactions to two mutually cis [BAr(F)](-) anions, and the other with mutually trans [BAr(F)](-) anions, giving 1D chain pol...Continue Reading

References

Jan 1, 1987·Annals of the New York Academy of Sciences·J S Cohen, R C Lyon
May 15, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Beatriz CorderoSantiago Alvarez
Sep 11, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·In-Hyeok ParkShim Sung Lee
Jun 28, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·William LevasonWenjian Zhang
Oct 2, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Paolo FarinaGillian Reid
Jan 12, 2013·Chemistry : a European Journal·Ignasi MonAnton Vidal-Ferran
May 2, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Santiago Alvarez
Jul 25, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Martin J D ChampionGillian Reid
Apr 25, 2014·Chemical Communications : Chem Comm·Matthew EverettGillian Reid
Dec 11, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Philip N BartlettPeter W Richardson
Feb 28, 2015·Inorganic Chemistry·Martin J D ChampionGillian Reid
May 15, 2015·Chemical Communications : Chem Comm·Marina CarravettaWenjian Zhang
Jun 27, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·John DykeLydia Rhyman

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Citations

Apr 14, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·William LevasonGillian Reid
Nov 4, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Yao-Pang ChangGillian Reid
Nov 20, 2021·Inorganic Chemistry·Miguel A SotoMark J MacLachlan

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