Tc(NX)Y3(Me2PhP)2 complexes (X = O or S; Y = Cl or Br). Preparation, characterization and EPR studies

Ulrich Abram; Reinhard Kirmse; Klaus Köhler; Bernd Lorenz; Lenzi Kaden

doi:10.1016/S0020-1693(00)85895-8

Tc(NX)Y₃(Me₂PhP)₂ complexes (X = O or S; Y = Cl or Br). Preparation, characterization and EPR studies

Ulrich Abram, Reinhard Kirmse, Klaus Köhler, Bernd Lorenz, Lenzi Kaden

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Abstract

The d⁵-'low-spin' Tc(II) complexes tribromonitrosyl-bis(dimethylphenylphosphine)technetium(II) and tribromo-thionitrosyl-bis(dimethylphenylphosphine)technetium(II) were prepared by ligand exchange starting from the analogous chloro compounds. The complexes were characterized chemically and IR, UVVis and EPR spectroscopically. In the room temperature EPR spectra a well-resolved ⁹⁹Tc hyperfine splitting is observed inidicating a ground state of the unpaired electron which is well separated from the other orbit states. The general features of the spectra at low temperatures are characteristic for an axially symmetric spin Hamiltonian. Analysis of the ⁹⁹Tc and ³¹P hfs (hfs = hyperfine splittings) shows a marked covalency of the Tcligand bonds. A comparison is given between the chloro and bromo, as well as between the nitrosyl and thionitrosyl complexes.

Original language	English
Pages (from-to)	15-20
Number of pages	6
Journal	Inorganica Chimica Acta
Volume	129
Issue number	1
DOIs	https://doi.org/10.1016/S0020-1693(00)85895-8
State	Published - 15 May 1987
Externally published	Yes

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title = "Tc(NX)Y3(Me2PhP)2 complexes (X = O or S; Y = Cl or Br). Preparation, characterization and EPR studies",

abstract = "The d5-'low-spin' Tc(II) complexes tribromonitrosyl-bis(dimethylphenylphosphine)technetium(II) and tribromo-thionitrosyl-bis(dimethylphenylphosphine)technetium(II) were prepared by ligand exchange starting from the analogous chloro compounds. The complexes were characterized chemically and IR, UVVis and EPR spectroscopically. In the room temperature EPR spectra a well-resolved 99Tc hyperfine splitting is observed inidicating a ground state of the unpaired electron which is well separated from the other orbit states. The general features of the spectra at low temperatures are characteristic for an axially symmetric spin Hamiltonian. Analysis of the 99Tc and 31P hfs (hfs = hyperfine splittings) shows a marked covalency of the Tcligand bonds. A comparison is given between the chloro and bromo, as well as between the nitrosyl and thionitrosyl complexes.",

author = "Ulrich Abram and Reinhard Kirmse and Klaus K{\"o}hler and Bernd Lorenz and Lenzi Kaden",

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T1 - Tc(NX)Y3(Me2PhP)2 complexes (X = O or S; Y = Cl or Br). Preparation, characterization and EPR studies

AU - Abram, Ulrich

AU - Kirmse, Reinhard

AU - Köhler, Klaus

AU - Lorenz, Bernd

AU - Kaden, Lenzi

PY - 1987/5/15

Y1 - 1987/5/15

N2 - The d5-'low-spin' Tc(II) complexes tribromonitrosyl-bis(dimethylphenylphosphine)technetium(II) and tribromo-thionitrosyl-bis(dimethylphenylphosphine)technetium(II) were prepared by ligand exchange starting from the analogous chloro compounds. The complexes were characterized chemically and IR, UVVis and EPR spectroscopically. In the room temperature EPR spectra a well-resolved 99Tc hyperfine splitting is observed inidicating a ground state of the unpaired electron which is well separated from the other orbit states. The general features of the spectra at low temperatures are characteristic for an axially symmetric spin Hamiltonian. Analysis of the 99Tc and 31P hfs (hfs = hyperfine splittings) shows a marked covalency of the Tcligand bonds. A comparison is given between the chloro and bromo, as well as between the nitrosyl and thionitrosyl complexes.

AB - The d5-'low-spin' Tc(II) complexes tribromonitrosyl-bis(dimethylphenylphosphine)technetium(II) and tribromo-thionitrosyl-bis(dimethylphenylphosphine)technetium(II) were prepared by ligand exchange starting from the analogous chloro compounds. The complexes were characterized chemically and IR, UVVis and EPR spectroscopically. In the room temperature EPR spectra a well-resolved 99Tc hyperfine splitting is observed inidicating a ground state of the unpaired electron which is well separated from the other orbit states. The general features of the spectra at low temperatures are characteristic for an axially symmetric spin Hamiltonian. Analysis of the 99Tc and 31P hfs (hfs = hyperfine splittings) shows a marked covalency of the Tcligand bonds. A comparison is given between the chloro and bromo, as well as between the nitrosyl and thionitrosyl complexes.

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U2 - 10.1016/S0020-1693(00)85895-8

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VL - 129

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EP - 20

JO - Inorganica Chimica Acta

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IS - 1

ER -

Tc(NX)Y₃(Me₂PhP)₂ complexes (X = O or S; Y = Cl or Br). Preparation, characterization and EPR studies

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