Coordination chemistry of selenoether macrocyclic ligands with transition metal ions
Coordination chemistry of selenoether macrocyclic ligands with transition metal ions
The complexes [M([8]aneSe2][PF6]2 were prepared by the reaction of MCl2 with two equivalents of [8]aneSe2 (1,5-diselenacyclooctane) and TlPF6 in MeCN, [M([8]aneSe2)Cl2] (M = Pt or Pd) by reaction of MCl2 with [8]aneSe2 in MeCN, and [M([8]aneSe2)Br2] (M = Pt or Pd) by the reaction of [MBr2(MeCN)2] and [8]aneSe2 in MeNO2. The single crystal X-ray structure of [Pd([8]aneSe2)Cl2]0.5MeNO2 reveals Pd(II) in a square planar geometry with an Se2Cl2 donor set, [8]aneSe2 adopting the chair-boat conformation. The complexes trans-[Pt([16]aneSe4)X2][PF6]2 (X = Cl or Br) and trans-[Pt([8]aneSe2)2Cl2][PF6]2 were prepared from the Pt(II) analogues and X2/CCl4. The single crystal X-ray structure of trans- [Pt([16]aneSe4)Cl2][PF6]2 shows an Se4Cl2 donor set; [16]aneSe4 adopts the up,up,down,down configuration. Treatment of MCl2 (M = Pd or Pt) with [24]aneSe6 (1,5,9,13,17,21-hexaselenacyclotetracosane) and TlPF6 affords the complexes [M([24]aneSe6)][PF6]2.
Reaction of CoX2 (X = Cl, Br or I) with [16]aneSe4 (1,5,9,13-tetraselenacyclohexadecane) and NH4PF6 (or NaBPH4 for X = Br) in MeNO2 yield the [Co([16]aneSe4)X2][Y] complexes. The [M([16]aneSe4)X2]+ species (M = Rh or Ir; X = Cl or Br) were prepared by reaction of MX3.3H2O and [16]aneSe4 in EtOH, or for [Rh([16]aneSe4)Br2]+, from [Rh(H2O)6]3+, LiBr and [16]aneSe4, and isolated by the addition of either NaBF4, NH4PF6 or NaBPh4. The compound [Rh([8]aneSe2)2Cl2][BF4] was prepared from [{Rh(CO)2Cl}2], [8]aneSe2 and HBF4 in Me2CO. The UV/vis and 59Co NMR studies on [Co([16]aneSe4)X2]+ reveal that for X = Cl or Br only trans dihalogeno species are present whilst cis and trans forms are present when X = I. 77Se-{1H} NMR studies on [M([16]aneSe4)X2]+ (M = Rh or Ir; X = Cl or Br) and [Rh([8]aneSe2)2Cl2}+ show the presence of both cis and trans forms in DMF solution, although for [M([16]aneSe4)Cl2]+ only the trans form is soluble in MeNO2. The single crystal X-ray structures of [M([16]aneSe4)Br2][BPh4] (M = Co or Ir) reveal Se4Br2 donor sets; [16]aneSe4 adopts the up,up,down,down configuration.
University of Southampton
1997
Quirk, Jeffrey
(1997)
Coordination chemistry of selenoether macrocyclic ligands with transition metal ions.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The complexes [M([8]aneSe2][PF6]2 were prepared by the reaction of MCl2 with two equivalents of [8]aneSe2 (1,5-diselenacyclooctane) and TlPF6 in MeCN, [M([8]aneSe2)Cl2] (M = Pt or Pd) by reaction of MCl2 with [8]aneSe2 in MeCN, and [M([8]aneSe2)Br2] (M = Pt or Pd) by the reaction of [MBr2(MeCN)2] and [8]aneSe2 in MeNO2. The single crystal X-ray structure of [Pd([8]aneSe2)Cl2]0.5MeNO2 reveals Pd(II) in a square planar geometry with an Se2Cl2 donor set, [8]aneSe2 adopting the chair-boat conformation. The complexes trans-[Pt([16]aneSe4)X2][PF6]2 (X = Cl or Br) and trans-[Pt([8]aneSe2)2Cl2][PF6]2 were prepared from the Pt(II) analogues and X2/CCl4. The single crystal X-ray structure of trans- [Pt([16]aneSe4)Cl2][PF6]2 shows an Se4Cl2 donor set; [16]aneSe4 adopts the up,up,down,down configuration. Treatment of MCl2 (M = Pd or Pt) with [24]aneSe6 (1,5,9,13,17,21-hexaselenacyclotetracosane) and TlPF6 affords the complexes [M([24]aneSe6)][PF6]2.
Reaction of CoX2 (X = Cl, Br or I) with [16]aneSe4 (1,5,9,13-tetraselenacyclohexadecane) and NH4PF6 (or NaBPH4 for X = Br) in MeNO2 yield the [Co([16]aneSe4)X2][Y] complexes. The [M([16]aneSe4)X2]+ species (M = Rh or Ir; X = Cl or Br) were prepared by reaction of MX3.3H2O and [16]aneSe4 in EtOH, or for [Rh([16]aneSe4)Br2]+, from [Rh(H2O)6]3+, LiBr and [16]aneSe4, and isolated by the addition of either NaBF4, NH4PF6 or NaBPh4. The compound [Rh([8]aneSe2)2Cl2][BF4] was prepared from [{Rh(CO)2Cl}2], [8]aneSe2 and HBF4 in Me2CO. The UV/vis and 59Co NMR studies on [Co([16]aneSe4)X2]+ reveal that for X = Cl or Br only trans dihalogeno species are present whilst cis and trans forms are present when X = I. 77Se-{1H} NMR studies on [M([16]aneSe4)X2]+ (M = Rh or Ir; X = Cl or Br) and [Rh([8]aneSe2)2Cl2}+ show the presence of both cis and trans forms in DMF solution, although for [M([16]aneSe4)Cl2]+ only the trans form is soluble in MeNO2. The single crystal X-ray structures of [M([16]aneSe4)Br2][BPh4] (M = Co or Ir) reveal Se4Br2 donor sets; [16]aneSe4 adopts the up,up,down,down configuration.
This record has no associated files available for download.
More information
Published date: 1997
Identifiers
Local EPrints ID: 462999
URI: http://eprints.soton.ac.uk/id/eprint/462999
PURE UUID: 86626e8b-44b5-46a5-b74f-b02dd8dbb328
Catalogue record
Date deposited: 04 Jul 2022 20:36
Last modified: 04 Jul 2022 20:36
Export record
Contributors
Author:
Jeffrey Quirk
Download statistics
Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.
View more statistics