Heterocyclic nitrogen donor complexes of aluminium, gallium and indium with weakly coordinating triflate anions
Heterocyclic nitrogen donor complexes of aluminium, gallium and indium with weakly coordinating triflate anions
The reactions of M(OTf)3 (M = Al, Ga, In; OTf = CF3SO3–) with 2,2′:6′,2′’- terpyridyl (terpy) in CH2Cl2 gave mer-[M(OTf)3(terpy)], whilst with 2,2′-bipyridyl (bipy) and 1,10-phenanthroline (phen) the products isolated were cis-[M”(OTf)2(bipy)2]OTf (M” = Al, Ga), cis-[In(OTf)(H2O)(bipy)2][OTf]2, cis-[Al(OTf)2(phen)2][OTf] and [In(H2O)2(phen)2][OTf]3. The X-ray structures of mer-[In(OTf)3(terpy)], cis-[Ga(OTf)2(bipy)2][OTf] and cis-[In(OTf)(H2O)(bipy)2][OTf]2, along with those of the minor by-products, cis-[Ga(H2O)2(phen)2][OTf]3 and the hydroxide-bridged dimer [{In(terpy)(OTf)}2(µ-OH)2][OTf]2 were also obtained, all of which show six-coordination at the metal ion. While the anhydrous complexes show κ1-coordination of the triflate to the metal ion, those species with coordinated water (or hydroxide) ligands show significant H-bonding interactions between the water H atoms and the O-atoms from triflate anions. The complexes were characterised by IR, 1H, 13C{1H}, 19F{1H} and 27Al NMR spectroscopy, together with microanalysis. The 19F{1H} NMR spectra suggest that in MeCN solution the coordinated triflates are displaced by the solvent, but the original complexes appear to reform on removal of the MeCN in vacuo.
2,2′:6′,2″- terpyridyl, Aluminium complexes, Diimine complexes, Gallium complexes, Indium complexes
Cairns, Kelsey R.
4d3b3ad3-d47a-4930-b55f-de1533c552a4
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
1 October 2021
Cairns, Kelsey R.
4d3b3ad3-d47a-4930-b55f-de1533c552a4
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Cairns, Kelsey R., Levason, William, Reid, Gillian and Zhang, Wenjian
(2021)
Heterocyclic nitrogen donor complexes of aluminium, gallium and indium with weakly coordinating triflate anions.
Polyhedron, 207, [115367].
(doi:10.1016/j.poly.2021.115367).
Abstract
The reactions of M(OTf)3 (M = Al, Ga, In; OTf = CF3SO3–) with 2,2′:6′,2′’- terpyridyl (terpy) in CH2Cl2 gave mer-[M(OTf)3(terpy)], whilst with 2,2′-bipyridyl (bipy) and 1,10-phenanthroline (phen) the products isolated were cis-[M”(OTf)2(bipy)2]OTf (M” = Al, Ga), cis-[In(OTf)(H2O)(bipy)2][OTf]2, cis-[Al(OTf)2(phen)2][OTf] and [In(H2O)2(phen)2][OTf]3. The X-ray structures of mer-[In(OTf)3(terpy)], cis-[Ga(OTf)2(bipy)2][OTf] and cis-[In(OTf)(H2O)(bipy)2][OTf]2, along with those of the minor by-products, cis-[Ga(H2O)2(phen)2][OTf]3 and the hydroxide-bridged dimer [{In(terpy)(OTf)}2(µ-OH)2][OTf]2 were also obtained, all of which show six-coordination at the metal ion. While the anhydrous complexes show κ1-coordination of the triflate to the metal ion, those species with coordinated water (or hydroxide) ligands show significant H-bonding interactions between the water H atoms and the O-atoms from triflate anions. The complexes were characterised by IR, 1H, 13C{1H}, 19F{1H} and 27Al NMR spectroscopy, together with microanalysis. The 19F{1H} NMR spectra suggest that in MeCN solution the coordinated triflates are displaced by the solvent, but the original complexes appear to reform on removal of the MeCN in vacuo.
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Accepted/In Press date: 9 July 2021
e-pub ahead of print date: 14 July 2021
Published date: 1 October 2021
Additional Information:
Funding Information:
We thank the EPSRC for funding via the ADEPT programme grant (EP/N035437/1) and EP/R513325/1.
Publisher Copyright:
© 2021
Copyright:
Copyright 2021 Elsevier B.V., All rights reserved.
Keywords:
2,2′:6′,2″- terpyridyl, Aluminium complexes, Diimine complexes, Gallium complexes, Indium complexes
Identifiers
Local EPrints ID: 450781
URI: http://eprints.soton.ac.uk/id/eprint/450781
ISSN: 0277-5387
PURE UUID: af194263-ac38-4148-9e24-8ceb1e4e1d7d
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Date deposited: 11 Aug 2021 16:31
Last modified: 18 Mar 2024 05:27
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Author:
Kelsey R. Cairns
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