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

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-diselenacyclo...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2015-01, Vol.44 (43), p.18748-18759
Main Authors: Champion, Martin J D, Levason, William, Pugh, David, Reid, Gillian
Format: Article
Language:English
Subjects:
Anions
Cations
Coordination compounds
Crystal structure
Distortion
Drying
Lithium
Macrocyclic compounds
Rubidium
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Summary: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 polymers. Solution multinuclear ((1)H, (13)C, (7)Li, (23)Na, (133)Cs) NMR data show that the macrocyclic coordination is retained in CH2Cl2 solution.
ISSN:1477-9226
1477-9234
DOI:10.1039/c5dt02583d