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Primary and secondary coordination of crown ethers to scandium(III). Synthesis, properties and structures of the reaction products of ScCl3(thf)(3), ScCl3?6H(2)O and Sc(NO3)(3)?5H(2)O with crown ethers

Primary and secondary coordination of crown ethers to scandium(III). Synthesis, properties and structures of the reaction products of ScCl3(thf)(3), ScCl3?6H(2)O and Sc(NO3)(3)?5H(2)O with crown ethers
Primary and secondary coordination of crown ethers to scandium(III). Synthesis, properties and structures of the reaction products of ScCl3(thf)(3), ScCl3?6H(2)O and Sc(NO3)(3)?5H(2)O with crown ethers
The synthesis and spectroscopic characterisation of [ScCl(15-crown-5)(MeCN)][SbCl6](2),[ScCl2(18-crown-6)][FeCl4] and [ScCl2([15]aneS(2)O(3))][FeCl4]([15]aneS(2)O(3) = 1,4-dithia-7,10,13-trioxacyclopentadecane) are reported, the last containing the first example of thioether-scandium(III) coordination. The structure of [ScCl(15-crown-5)( MeCN)] [SbCl6](2) reveals a pentagonal bipyramidal cation with axial Cl and MeCN, whilst [ScCl2(18-crown-6)][FeCl4] is also pentagonal bipyramidal with axial Cl ligands. H-1 and Sc-45 NMR spectroscopies have been used to study the speciation in the ScCl3/18-crown-6 system in the presence of the Lewis acids SbCl5 and FeCl3 in anhydrous MeCN. Hydrolysis of any of the above complexes and of [Sc(12-crown-4)2](3+) (formed from ScCl3(thf)(3), crown and SbCl5), results in the formation of [ScCl3(H2O)(3)].crown,the solution NMR spectra of which show a common scandium species and uncomplexed crown ether. The structure of [ScCl3(H2O)(3)].18-crown-6 reveals a mer octahedral scandium species which is hydrogen bonded via the scandium-coordinated water to the 18-crown-6 (secondary coordination) leading to infinite chains. Similar complexes have been isolated directly from reaction of ScCl3.6H(2)O and the crown ethers in absolute ethanol, including [ScCl3(H2O)(3)](n).(crown) (n = 1 or 2, crown = 18-crown-6; n = 2, crown = 15-crown-5 or 12-crown-4). Hydrated scandium nitrate and the crown ethers react in ethanol solution to form a surprisingly diverse range of structural types containing the crown ethers hydrogen bonded to the scandium-aquo-nitrato or scandium-aquo-hydroxo-nitrato complexes. X-Ray crystal structures are reported for [Sc(H2O)(2)(NO3)(3)].(12-crown-4)(2), [Sc(H2O)(4)(NO3)(2)]NO3.15-crown-5 and [Sc-2(NO3)(2)(H2O)(6)(OH)(2)](NO3)(2).12-crown-4. However, in the related [Sc-2(NO3)(4)(H2O)(4)(OH)(2)][Na(12-crown-4)(2)](NO3).(H2O)(3) the hydrogen bonding occurs between the lattice water and the scandium dimer unit.
crystal-structures, spectroscopic characterization, sphere coordination, complexes, chemistry, sc-45, 15-crown-5, nitrates
0300-9246
857-865
Brown, Michael D.
76a42341-1a1e-4ec9-8cdc-aca9d5e53bf4
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Murray, David C.
d376ac03-5132-4d5a-9826-5abc5959573f
Popham, Michael C.
7f17dd46-c115-4839-a462-442c7b8f82af
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Brown, Michael D.
76a42341-1a1e-4ec9-8cdc-aca9d5e53bf4
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Murray, David C.
d376ac03-5132-4d5a-9826-5abc5959573f
Popham, Michael C.
7f17dd46-c115-4839-a462-442c7b8f82af
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7

Brown, Michael D., Levason, William, Murray, David C., Popham, Michael C., Reid, Gillian and Webster, Michael (2003) Primary and secondary coordination of crown ethers to scandium(III). Synthesis, properties and structures of the reaction products of ScCl3(thf)(3), ScCl3?6H(2)O and Sc(NO3)(3)?5H(2)O with crown ethers. Dalton Transactions, (5), 857-865. (doi:10.1039/b210458j).

Record type: Article

Abstract

The synthesis and spectroscopic characterisation of [ScCl(15-crown-5)(MeCN)][SbCl6](2),[ScCl2(18-crown-6)][FeCl4] and [ScCl2([15]aneS(2)O(3))][FeCl4]([15]aneS(2)O(3) = 1,4-dithia-7,10,13-trioxacyclopentadecane) are reported, the last containing the first example of thioether-scandium(III) coordination. The structure of [ScCl(15-crown-5)( MeCN)] [SbCl6](2) reveals a pentagonal bipyramidal cation with axial Cl and MeCN, whilst [ScCl2(18-crown-6)][FeCl4] is also pentagonal bipyramidal with axial Cl ligands. H-1 and Sc-45 NMR spectroscopies have been used to study the speciation in the ScCl3/18-crown-6 system in the presence of the Lewis acids SbCl5 and FeCl3 in anhydrous MeCN. Hydrolysis of any of the above complexes and of [Sc(12-crown-4)2](3+) (formed from ScCl3(thf)(3), crown and SbCl5), results in the formation of [ScCl3(H2O)(3)].crown,the solution NMR spectra of which show a common scandium species and uncomplexed crown ether. The structure of [ScCl3(H2O)(3)].18-crown-6 reveals a mer octahedral scandium species which is hydrogen bonded via the scandium-coordinated water to the 18-crown-6 (secondary coordination) leading to infinite chains. Similar complexes have been isolated directly from reaction of ScCl3.6H(2)O and the crown ethers in absolute ethanol, including [ScCl3(H2O)(3)](n).(crown) (n = 1 or 2, crown = 18-crown-6; n = 2, crown = 15-crown-5 or 12-crown-4). Hydrated scandium nitrate and the crown ethers react in ethanol solution to form a surprisingly diverse range of structural types containing the crown ethers hydrogen bonded to the scandium-aquo-nitrato or scandium-aquo-hydroxo-nitrato complexes. X-Ray crystal structures are reported for [Sc(H2O)(2)(NO3)(3)].(12-crown-4)(2), [Sc(H2O)(4)(NO3)(2)]NO3.15-crown-5 and [Sc-2(NO3)(2)(H2O)(6)(OH)(2)](NO3)(2).12-crown-4. However, in the related [Sc-2(NO3)(4)(H2O)(4)(OH)(2)][Na(12-crown-4)(2)](NO3).(H2O)(3) the hydrogen bonding occurs between the lattice water and the scandium dimer unit.

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Published date: 2003
Keywords: crystal-structures, spectroscopic characterization, sphere coordination, complexes, chemistry, sc-45, 15-crown-5, nitrates

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Local EPrints ID: 19915
URI: https://eprints.soton.ac.uk/id/eprint/19915
ISSN: 0300-9246
PURE UUID: 1f78f8a9-d8f9-474e-90fe-11eeb8b09d59
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 22 Feb 2006
Last modified: 20 Jul 2019 01:28

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Contributors

Author: Michael D. Brown
Author: William Levason ORCID iD
Author: David C. Murray
Author: Michael C. Popham
Author: Gillian Reid ORCID iD
Author: Michael Webster

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