Cobalt half-sandwich, sandwich, and mixed sandwich complexes with soft tripodal ligands

C.A. Dodds, M.A. Lehmann, J.F. Ojo, J. Reglinski, M.D. Spicer

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

Reaction of sodium hydrotris(methimazolyl)borate (NaTmMe) with cobalt halides leads to the formation of paramagnetic pseudotetrahedral [Co(Tm-Me)X] (X = Cl, Br, I), of which the bromide has been crystallographically characterized. Mass spectrometry reveals the presence of higher molecular weight fragments [Co(Tm-Me)(2)](+) and [Co-2(Tm-Me)(2)X](+) in solution. Aerial oxidation in donor solvents (e.g. MeCN) leads to formation of the [Co(Tm-Me)(2)](+) cation, which has been crystallographically characterized as the BF4-, ClO4-, Br-, and I-, salts. Attempts to prepare the mixed sandwich complex, [Co(Cp)(Tm-Me)](+), resulted in ligand decomposition to yield [Co(mtH)(3)I]I (mtH = 1-methylimidazole-2-thione), but with the more electron donating methylcyclopentadienyl (Cp-Me) ligand, [Co(Cp-Me)(Tm-Me)]I was isolated and characterized. Electrochemical measurements reveal that the cobalt(III) Tm-Me complexes are consistently more difficult to reduce than their Tp and Cp congeners.
LanguageEnglish
Pages4927-4934
Number of pages7
JournalInorganic Chemistry
Volume43
Issue number16
DOIs
Publication statusPublished - 9 Aug 2004

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Cobalt
cobalt
Ligands
Thiones
congeners
Borates
ligands
borates
Bromides
halides
Mass spectrometry
Cations
bromides
molecular weight
mass spectroscopy
Salts
Sodium
Molecular weight
fragments
sodium

Keywords

  • ORGANOMETALLIC CHEMISTRY
  • TRANSITION-METALS
  • CYCLOPENTADIENYL
  • NICKEL(II)
  • FIELD
  • IRON
  • TM

Cite this

Dodds, C.A. ; Lehmann, M.A. ; Ojo, J.F. ; Reglinski, J. ; Spicer, M.D. / Cobalt half-sandwich, sandwich, and mixed sandwich complexes with soft tripodal ligands. In: Inorganic Chemistry. 2004 ; Vol. 43, No. 16. pp. 4927-4934.
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Cobalt half-sandwich, sandwich, and mixed sandwich complexes with soft tripodal ligands. / Dodds, C.A.; Lehmann, M.A.; Ojo, J.F.; Reglinski, J.; Spicer, M.D.

In: Inorganic Chemistry, Vol. 43, No. 16, 09.08.2004, p. 4927-4934.

Research output: Contribution to journalArticle

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T1 - Cobalt half-sandwich, sandwich, and mixed sandwich complexes with soft tripodal ligands

AU - Dodds, C.A.

AU - Lehmann, M.A.

AU - Ojo, J.F.

AU - Reglinski, J.

AU - Spicer, M.D.

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N2 - Reaction of sodium hydrotris(methimazolyl)borate (NaTmMe) with cobalt halides leads to the formation of paramagnetic pseudotetrahedral [Co(Tm-Me)X] (X = Cl, Br, I), of which the bromide has been crystallographically characterized. Mass spectrometry reveals the presence of higher molecular weight fragments [Co(Tm-Me)(2)](+) and [Co-2(Tm-Me)(2)X](+) in solution. Aerial oxidation in donor solvents (e.g. MeCN) leads to formation of the [Co(Tm-Me)(2)](+) cation, which has been crystallographically characterized as the BF4-, ClO4-, Br-, and I-, salts. Attempts to prepare the mixed sandwich complex, [Co(Cp)(Tm-Me)](+), resulted in ligand decomposition to yield [Co(mtH)(3)I]I (mtH = 1-methylimidazole-2-thione), but with the more electron donating methylcyclopentadienyl (Cp-Me) ligand, [Co(Cp-Me)(Tm-Me)]I was isolated and characterized. Electrochemical measurements reveal that the cobalt(III) Tm-Me complexes are consistently more difficult to reduce than their Tp and Cp congeners.

AB - Reaction of sodium hydrotris(methimazolyl)borate (NaTmMe) with cobalt halides leads to the formation of paramagnetic pseudotetrahedral [Co(Tm-Me)X] (X = Cl, Br, I), of which the bromide has been crystallographically characterized. Mass spectrometry reveals the presence of higher molecular weight fragments [Co(Tm-Me)(2)](+) and [Co-2(Tm-Me)(2)X](+) in solution. Aerial oxidation in donor solvents (e.g. MeCN) leads to formation of the [Co(Tm-Me)(2)](+) cation, which has been crystallographically characterized as the BF4-, ClO4-, Br-, and I-, salts. Attempts to prepare the mixed sandwich complex, [Co(Cp)(Tm-Me)](+), resulted in ligand decomposition to yield [Co(mtH)(3)I]I (mtH = 1-methylimidazole-2-thione), but with the more electron donating methylcyclopentadienyl (Cp-Me) ligand, [Co(Cp-Me)(Tm-Me)]I was isolated and characterized. Electrochemical measurements reveal that the cobalt(III) Tm-Me complexes are consistently more difficult to reduce than their Tp and Cp congeners.

KW - ORGANOMETALLIC CHEMISTRY

KW - TRANSITION-METALS

KW - CYCLOPENTADIENYL

KW - NICKEL(II)

KW - FIELD

KW - IRON

KW - TM

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T2 - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

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ER -