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Arsenic(III) halide complexes with acyclic and macrocyclic thio- and selenoether coligands: synthesis and structural properties

Arsenic(III) halide complexes with acyclic and macrocyclic thio- and selenoether coligands: synthesis and structural properties
Arsenic(III) halide complexes with acyclic and macrocyclic thio- and selenoether coligands: synthesis and structural properties
The preparations of the new complexes [AsBr3{MeS(CH2)(2)SMe}], [ASX(3)([9]aneS(3))] (X = Cl, Br or I; [9]aneS(3) = 1,4,7-trithiacyclononane), [AsCl3([14]aneS(4))] ([14]aneS(4) = 1,4,8,11 -tetrathiacyclotetradecane), [AsX3([8]aneSe(2))] ([8]-aneSe(2) = 1,5-diselenacyclooctane), [(AsX3)(2)([16]aneSe(4))] ([16]aneSe(4) = 1,5,9,13-tetraselenacyclohexadecane), and [(AsBr3)(2)([24]aneSe(6))] ([24]aneSe(6) = 1,5,9,13,17,21-hexaselenacyclotetracosane) are described, These are obtained from direct reaction of the appropriate AsX3 and 1 mol equiv of the thio- or selenoether ligand in anhydrous CH2Cl2 (or thf for X = I) solution. The products have been characterized by microanalysis and IR and H-1 NMR spectroscopy. In solution they are extensively dissociated, reflecting the weak Lewis acidity of ASX3. Reaction of AsX3 with MeSe(CH2)(2)SeMe or MeC(CH2EMe)(3) (E = S or Se) gave only oils, Treatment of PCl3 or PBr3 with Me2S, MeE(CH2)(2)EMe, or [9]aneS(3) failed to give solid complexes, and there was no evidence from NMR spectroscopy for any adduct formation in solution. The crystal structures of the first series of thioether and selenoether complexes of As(III) are described: [AsBr3{MeS(CH2)(2)SMe}], C4H10AsBr3S2, a = 10.2818(6) Angstrom, b = 7.8014(5) Angstrom, c = 14.503(1) Angstrom, beta = 102.9330(2)degrees, monoclinic, P2(1)/c, Z = 4; [AsI3{MeS(CH2)(2)SMe}], C4H10AsI3S2, a = 9.1528(1) Angstrom, b = 11.5622(2) Angstrom, c = 12,0939(2) Angstrom, beta= 93,863(1)degrees, monoclinic, P2(1)/n, Z = 4; [AsCl3([9]aneS(3))b C6H12AsCl3S3, a = 17.520(4) Angstrom, b = 17.520(4) Angstrom, c = 16.790(7) Angstrom, tetragonal, /4(1)cd, Z = 16; [AsCl3([14]aneS(4))], C10H20AsCl3S4 a = 13.5942(2) Angstrom, b = 7.7007(1) Angstrom, c = 18.1270(3) Angstrom, beta = 111.1662(5)degrees, monoclinic, P2(1)/n, Z = 4; [(AsCl3)(2)([16]-aneSe(4))], C12H24As2Cl6Se4, a = 9.764(3) Angstrom, b = 13.164(1) Angstrom, c = 10.627(2) Angstrom, beta = 114,90(1)degrees, monoclinic, P2(1)/n, Z = 2; [(AsBr3)(2)([16]aneSe(4))], C12H24As2Br6Se4, a = 10.1220(1) Angstrom, b = 13.4494(2) Angstrom, c = 10.5125(2) Angstrom, beta = 113.49(2)degrees, monoclinic, P2(1)/n, Z = 2. [AsBr3{MeS(CH2)(2)SMe}] and [AsI3 MeS(CH2)(2)SMe}] reveal discrete mu(2)- halo As2X6 climeric structures involving distorted octahedral As(III), with the dithioether ligand chelating, [ASCl(3)([9]-aneS(3))] adopts a discrete molecular distorted octahedral geometry with the thioether behaving as a weakly coordinated fac-capping ligand, [AsCl3([14]aneS(4))] forms an infinite sheet involving two mu(2)-chloro ligands on each As but bridging to two distinct As centers. Each macrocycle coordinates to two adjacent As centers via one S atom, giving a cis-octahedral C14S2 donor set at As(III), The structures of [(AsCl3)(2)([16]aneSe(4))] and [(AsBr3)(2)([16]aneSe(4))] adopt 2-dimensional sheet structures with mu(2)-dihalo As2X6 dimers cross-linked by mu(4)-tetraselenoether macrocycles, giving a disorted cis-X4Se2 donor set at each As center. These species are compared with their antimony(III) and bismuth(III) analogues where appropriate.
crystal-structure, ligands
0020-1669
2070-2076
Hill, Nicholas J.
c588ad7e-5668-46b9-b84a-791b664f37aa
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Hill, Nicholas J.
c588ad7e-5668-46b9-b84a-791b664f37aa
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037

Hill, Nicholas J., Levason, William and Reid, Gillian (2002) Arsenic(III) halide complexes with acyclic and macrocyclic thio- and selenoether coligands: synthesis and structural properties. Inorganic Chemistry, 41 (8), 2070-2076. (doi:10.1021/ic011139t).

Record type: Article

Abstract

The preparations of the new complexes [AsBr3{MeS(CH2)(2)SMe}], [ASX(3)([9]aneS(3))] (X = Cl, Br or I; [9]aneS(3) = 1,4,7-trithiacyclononane), [AsCl3([14]aneS(4))] ([14]aneS(4) = 1,4,8,11 -tetrathiacyclotetradecane), [AsX3([8]aneSe(2))] ([8]-aneSe(2) = 1,5-diselenacyclooctane), [(AsX3)(2)([16]aneSe(4))] ([16]aneSe(4) = 1,5,9,13-tetraselenacyclohexadecane), and [(AsBr3)(2)([24]aneSe(6))] ([24]aneSe(6) = 1,5,9,13,17,21-hexaselenacyclotetracosane) are described, These are obtained from direct reaction of the appropriate AsX3 and 1 mol equiv of the thio- or selenoether ligand in anhydrous CH2Cl2 (or thf for X = I) solution. The products have been characterized by microanalysis and IR and H-1 NMR spectroscopy. In solution they are extensively dissociated, reflecting the weak Lewis acidity of ASX3. Reaction of AsX3 with MeSe(CH2)(2)SeMe or MeC(CH2EMe)(3) (E = S or Se) gave only oils, Treatment of PCl3 or PBr3 with Me2S, MeE(CH2)(2)EMe, or [9]aneS(3) failed to give solid complexes, and there was no evidence from NMR spectroscopy for any adduct formation in solution. The crystal structures of the first series of thioether and selenoether complexes of As(III) are described: [AsBr3{MeS(CH2)(2)SMe}], C4H10AsBr3S2, a = 10.2818(6) Angstrom, b = 7.8014(5) Angstrom, c = 14.503(1) Angstrom, beta = 102.9330(2)degrees, monoclinic, P2(1)/c, Z = 4; [AsI3{MeS(CH2)(2)SMe}], C4H10AsI3S2, a = 9.1528(1) Angstrom, b = 11.5622(2) Angstrom, c = 12,0939(2) Angstrom, beta= 93,863(1)degrees, monoclinic, P2(1)/n, Z = 4; [AsCl3([9]aneS(3))b C6H12AsCl3S3, a = 17.520(4) Angstrom, b = 17.520(4) Angstrom, c = 16.790(7) Angstrom, tetragonal, /4(1)cd, Z = 16; [AsCl3([14]aneS(4))], C10H20AsCl3S4 a = 13.5942(2) Angstrom, b = 7.7007(1) Angstrom, c = 18.1270(3) Angstrom, beta = 111.1662(5)degrees, monoclinic, P2(1)/n, Z = 4; [(AsCl3)(2)([16]-aneSe(4))], C12H24As2Cl6Se4, a = 9.764(3) Angstrom, b = 13.164(1) Angstrom, c = 10.627(2) Angstrom, beta = 114,90(1)degrees, monoclinic, P2(1)/n, Z = 2; [(AsBr3)(2)([16]aneSe(4))], C12H24As2Br6Se4, a = 10.1220(1) Angstrom, b = 13.4494(2) Angstrom, c = 10.5125(2) Angstrom, beta = 113.49(2)degrees, monoclinic, P2(1)/n, Z = 2. [AsBr3{MeS(CH2)(2)SMe}] and [AsI3 MeS(CH2)(2)SMe}] reveal discrete mu(2)- halo As2X6 climeric structures involving distorted octahedral As(III), with the dithioether ligand chelating, [ASCl(3)([9]-aneS(3))] adopts a discrete molecular distorted octahedral geometry with the thioether behaving as a weakly coordinated fac-capping ligand, [AsCl3([14]aneS(4))] forms an infinite sheet involving two mu(2)-chloro ligands on each As but bridging to two distinct As centers. Each macrocycle coordinates to two adjacent As centers via one S atom, giving a cis-octahedral C14S2 donor set at As(III), The structures of [(AsCl3)(2)([16]aneSe(4))] and [(AsBr3)(2)([16]aneSe(4))] adopt 2-dimensional sheet structures with mu(2)-dihalo As2X6 dimers cross-linked by mu(4)-tetraselenoether macrocycles, giving a disorted cis-X4Se2 donor set at each As center. These species are compared with their antimony(III) and bismuth(III) analogues where appropriate.

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Published date: 22 April 2002
Keywords: crystal-structure, ligands

Identifiers

Local EPrints ID: 19776
URI: http://eprints.soton.ac.uk/id/eprint/19776
ISSN: 0020-1669
PURE UUID: c695943a-ad3e-44d2-92f0-005298976389
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: 20 Feb 2006
Last modified: 09 Jan 2022 02:43

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Contributors

Author: Nicholas J. Hill
Author: William Levason ORCID iD
Author: Gillian Reid ORCID iD

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