Abstract
| Original language | English |
|---|---|
| Pages (from-to) | 4927-4934 |
| Number of pages | 7 |
| Journal | Inorganic Chemistry |
| Volume | 43 |
| Issue number | 16 |
| DOIs | |
| Publication status | Published - 9 Aug 2004 |
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Keywords
- ORGANOMETALLIC CHEMISTRY
- TRANSITION-METALS
- CYCLOPENTADIENYL
- NICKEL(II)
- FIELD
- IRON
- TM
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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 journal › Article
TY - JOUR
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.
PY - 2004/8/9
Y1 - 2004/8/9
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
UR - http://pubs.acs.org/cgi-bin/article.cgi/inocaj/2004/43/i16/pdf/ic0496525.pdf
UR - http://dx.doi.org/10.1021/ic0496525
U2 - 10.1021/ic0496525
DO - 10.1021/ic0496525
M3 - Article
VL - 43
SP - 4927
EP - 4934
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 16
ER -