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Synthesis and properties of antimony(III) and bismuth(III) halide complexes of diphosphines and diarsines. Crystal structures of Bi2I6{o-C6H4(AsMe2)(2)}(2) , Sb2Br6{o-C6H4(PPh2)(2)}(2) , Sb2Cl6{o-C6H4(AsMe2)(2)} , and BiCl3{o-C6H4(P(O)Ph-2)(2)}(thf)

Synthesis and properties of antimony(III) and bismuth(III) halide complexes of diphosphines and diarsines. Crystal structures of Bi2I6{o-C6H4(AsMe2)(2)}(2) , Sb2Br6{o-C6H4(PPh2)(2)}(2) , Sb2Cl6{o-C6H4(AsMe2)(2)} , and BiCl3{o-C6H4(P(O)Ph-2)(2)}(thf)
Synthesis and properties of antimony(III) and bismuth(III) halide complexes of diphosphines and diarsines. Crystal structures of Bi2I6{o-C6H4(AsMe2)(2)}(2) , Sb2Br6{o-C6H4(PPh2)(2)}(2) , Sb2Cl6{o-C6H4(AsMe2)(2)} , and BiCl3{o-C6H4(P(O)Ph-2)(2)}(thf)
The reaction of SbX3 or BiX3 (X=Cl, Br or I) with the diarsines o-C6H4(AsMe2)(2) or Ph2AsCH2CH2AsPh2, the triarsine MeC(CH2AsMe2)(3), or the diphosphines o-C6H4(PMe2)(2) or o-C6H4(PPh2)(2) (L), yield complexes of 1:1 stoichiometry MX3L irrespective of the reactant ratios used. X-Ray structures of [Bi2I6{o-C6H4(AsMe2)(2)}(2)] and [Sb2Br6{o-C6H4(PPh2)(2)}(2)] reveal distorted octahedral Bi or Sb coordination spheres, linked via asymmetric halide-bridges. Bond lengths suggest a bonding model based upon primary bonding in pyramidal MX3 groups with weaker secondary interactions to the diphosphine or diarsine and the longer distance bridging halide. [Sb2Cl6{o-C6H4(AsMe2)(2)}] is obtained by partial decomposition of [Sb2Cl6{o-C6H4(AsMe2)(2)}(2)] in hot ethanol and contains Sb{o-C6H4(AsMe2)(2)}Cl-2 and SbCl4 units linked via asymmetric chlorine bridges into puckered chains, which associate further through long Sb . . . Cl contacts to produce a polymeric sheet structure. The mononuclear species [BiCl3{o-C6H4(P(O)Ph-2)(2)}(thf)] obtained from BiCl3 and o-C6H4(P(O)Ph-2)(2) in thf is a distorted octahedron with a BiCl3O3 donor set.
phosphine complexes, ligands, coordination
1477-9226
1007-1012
Genge, A.R.J.
5c91d7e3-30c7-449e-b88b-0b369d3afb21
Hill, N.J.
986215d5-16c9-45a8-b8b7-27c2c48a293a
Levason, W.
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, G.
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Genge, A.R.J.
5c91d7e3-30c7-449e-b88b-0b369d3afb21
Hill, N.J.
986215d5-16c9-45a8-b8b7-27c2c48a293a
Levason, W.
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, G.
37d35b11-40ce-48c5-a68e-f6ce04cd4037

Genge, A.R.J., Hill, N.J., Levason, W. and Reid, G. (2001) Synthesis and properties of antimony(III) and bismuth(III) halide complexes of diphosphines and diarsines. Crystal structures of Bi2I6{o-C6H4(AsMe2)(2)}(2) , Sb2Br6{o-C6H4(PPh2)(2)}(2) , Sb2Cl6{o-C6H4(AsMe2)(2)} , and BiCl3{o-C6H4(P(O)Ph-2)(2)}(thf). Dalton Transactions, (7), 1007-1012. (doi:10.1039/b010179f).

Record type: Article

Abstract

The reaction of SbX3 or BiX3 (X=Cl, Br or I) with the diarsines o-C6H4(AsMe2)(2) or Ph2AsCH2CH2AsPh2, the triarsine MeC(CH2AsMe2)(3), or the diphosphines o-C6H4(PMe2)(2) or o-C6H4(PPh2)(2) (L), yield complexes of 1:1 stoichiometry MX3L irrespective of the reactant ratios used. X-Ray structures of [Bi2I6{o-C6H4(AsMe2)(2)}(2)] and [Sb2Br6{o-C6H4(PPh2)(2)}(2)] reveal distorted octahedral Bi or Sb coordination spheres, linked via asymmetric halide-bridges. Bond lengths suggest a bonding model based upon primary bonding in pyramidal MX3 groups with weaker secondary interactions to the diphosphine or diarsine and the longer distance bridging halide. [Sb2Cl6{o-C6H4(AsMe2)(2)}] is obtained by partial decomposition of [Sb2Cl6{o-C6H4(AsMe2)(2)}(2)] in hot ethanol and contains Sb{o-C6H4(AsMe2)(2)}Cl-2 and SbCl4 units linked via asymmetric chlorine bridges into puckered chains, which associate further through long Sb . . . Cl contacts to produce a polymeric sheet structure. The mononuclear species [BiCl3{o-C6H4(P(O)Ph-2)(2)}(thf)] obtained from BiCl3 and o-C6H4(P(O)Ph-2)(2) in thf is a distorted octahedron with a BiCl3O3 donor set.

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Published date: 2001
Keywords: phosphine complexes, ligands, coordination

Identifiers

Local EPrints ID: 19494
URI: http://eprints.soton.ac.uk/id/eprint/19494
ISSN: 1477-9226
PURE UUID: 6186d317-6e93-4576-b6e2-8a91c3e60079
ORCID for W. Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for G. Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 16 Feb 2006
Last modified: 15 Dec 2018 01:36

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Contributors

Author: A.R.J. Genge
Author: N.J. Hill
Author: W. Levason ORCID iD
Author: G. Reid ORCID iD

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