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Complexes of Group 2 dications with soft thioether- and selenoether-containing macrocycles

Complexes of Group 2 dications with soft thioether- and selenoether-containing macrocycles
Complexes of Group 2 dications with soft thioether- and selenoether-containing macrocycles
A new route to cationic complexes of Mg, Ca, Sr and Ba with 18-membered ring O4S2, O4Se2 and O2S4 donor macrocycles from metal acetonitrile complexes with weakly coordinating [BArF]? anions is described. The precursors used were [M(MeCN)x][BArF]2 (M = Mg, x = 6; M = Ca, x = 8) and [M?(acacH)(MeCN)5][BArF]2 (M? = Sr or Ba). Reaction of these with the heterocrowns, [18]aneO4S2 (1,4,10,13-tetraoxa-7,16-dithiacyclooctadecane), [18]aneO4Se2 (1,4,10,13-tetraoxa-7,16-diselenacyclooctadecane) or [18]aneO2S4 (1,10-dioxa-4,7,13,16-tetrathiacyclooctadecane) in anhydrous CH2Cl2 solution gave [M(heterocrown)(MeCN)2][BArF]2 for M = Mg, Ca or Sr, whilst the larger Ba forms [Ba(heterocrown)(acacH)(MeCN)][BArF]2. The complexes have been characterised by microanalysis, IR, 1H and 13C{1H} NMR spectroscopy. X-ray crystal structures are reported for [Ca([18]aneO2S4)(MeCN)2][BArF]2, [Ca([18]aneO4Se2)(MeCN)2][BArF]2, [Sr([18]aneO4S2)(MeCN)2][BArF]2, and [Sr([18]aneO4Se2)(MeCN)2][BArF]2 which contain 8-coordinate metal centres with trans-nitrile ligands and ?6-heterocrowns, and for the 9-coordinate [Ba([18]aneO4Se2)(acacH)(MeCN)][BArF]2. Adventitious hydrolysis of the magnesium complexes in solution results in six-coordinate complexes, [Mg(?3-[18]aneO4Se2)(OH2)2(MeCN)][BArF]2 and [Mg(?3-[18]aneO4S2)(OH2)2(MeCN)][BArF]2, whose structures were determined. X-ray crystal structures are also reported for [Mg(MeCN)6][BArF]2, [M(MeCN)8][BArF]2 (M = Ca, Sr) and [Ca(18-crown-6)(MeCN)2][BArF]2
0300-9246
7900-7911
Levason, William
1aee0faa-cd59-4d06-bb7a-9a25a0a561ab
Pugh, David
33c2663d-b70d-4366-8f0a-8765713b25ad
Purkis, Jamie M.
17c76efb-2aa2-429e-92b3-5a21de7b02a5
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Levason, William
1aee0faa-cd59-4d06-bb7a-9a25a0a561ab
Pugh, David
33c2663d-b70d-4366-8f0a-8765713b25ad
Purkis, Jamie M.
17c76efb-2aa2-429e-92b3-5a21de7b02a5
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037

Levason, William, Pugh, David, Purkis, Jamie M. and Reid, Gillian (2016) Complexes of Group 2 dications with soft thioether- and selenoether-containing macrocycles. Dalton Transactions, 45 (18), 7900-7911. (doi:10.1039/c6dt00808a).

Record type: Article

Abstract

A new route to cationic complexes of Mg, Ca, Sr and Ba with 18-membered ring O4S2, O4Se2 and O2S4 donor macrocycles from metal acetonitrile complexes with weakly coordinating [BArF]? anions is described. The precursors used were [M(MeCN)x][BArF]2 (M = Mg, x = 6; M = Ca, x = 8) and [M?(acacH)(MeCN)5][BArF]2 (M? = Sr or Ba). Reaction of these with the heterocrowns, [18]aneO4S2 (1,4,10,13-tetraoxa-7,16-dithiacyclooctadecane), [18]aneO4Se2 (1,4,10,13-tetraoxa-7,16-diselenacyclooctadecane) or [18]aneO2S4 (1,10-dioxa-4,7,13,16-tetrathiacyclooctadecane) in anhydrous CH2Cl2 solution gave [M(heterocrown)(MeCN)2][BArF]2 for M = Mg, Ca or Sr, whilst the larger Ba forms [Ba(heterocrown)(acacH)(MeCN)][BArF]2. The complexes have been characterised by microanalysis, IR, 1H and 13C{1H} NMR spectroscopy. X-ray crystal structures are reported for [Ca([18]aneO2S4)(MeCN)2][BArF]2, [Ca([18]aneO4Se2)(MeCN)2][BArF]2, [Sr([18]aneO4S2)(MeCN)2][BArF]2, and [Sr([18]aneO4Se2)(MeCN)2][BArF]2 which contain 8-coordinate metal centres with trans-nitrile ligands and ?6-heterocrowns, and for the 9-coordinate [Ba([18]aneO4Se2)(acacH)(MeCN)][BArF]2. Adventitious hydrolysis of the magnesium complexes in solution results in six-coordinate complexes, [Mg(?3-[18]aneO4Se2)(OH2)2(MeCN)][BArF]2 and [Mg(?3-[18]aneO4S2)(OH2)2(MeCN)][BArF]2, whose structures were determined. X-ray crystal structures are also reported for [Mg(MeCN)6][BArF]2, [M(MeCN)8][BArF]2 (M = Ca, Sr) and [Ca(18-crown-6)(MeCN)2][BArF]2

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Accepted/In Press date: 25 March 2016
e-pub ahead of print date: 1 April 2016
Published date: 14 May 2016
Organisations: Chemistry

Identifiers

Local EPrints ID: 398638
URI: http://eprints.soton.ac.uk/id/eprint/398638
ISSN: 0300-9246
PURE UUID: 69014ae2-f568-4027-b403-de8a89624dcc
ORCID for Jamie M. Purkis: ORCID iD orcid.org/0000-0002-6387-1220
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 28 Jul 2016 14:02
Last modified: 02 Jul 2021 02:03

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