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

Christopher A. Dodds; Mario Alexander Lehmann; Jonathan F. Ojo; John Reglinski; Mark D. Spicer

doi:10.1021/ic0496525

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

Christopher A. Dodds, Mario Alexander Lehmann, Jonathan F. Ojo, John Reglinski^*, Mark D. Spicer

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

30 Citations (Scopus)

Abstract

Reaction of sodium hydrotris(methimazolyl)borate (NaTm^Me) with cobalt halides leads to the formation of paramagnetic pseudotetrahedral [Co(Tm^Me)X] (X = CI, 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 [Co₂(Tm^Me)₂X]⁺ 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^-, C1O ₄^-, Br^-, and I^-, salts. Attempts to prepare the mixed sandwich complex, [Co(Cp)(Tm^Me)]⁺, resulted in ligand decomposition to yield [Co(mtH)₃I]I (mtH = 1-methylimidazole-2-thione), but with the more electron donating methylcyclopentadienyl (Cp^Me) ligand, [Co(Cp^Me)(Tm ^Me)]l 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.

Original language	English
Pages (from-to)	4927-4934
Number of pages	8
Journal	Inorganic Chemistry
Volume	43
Issue number	16
Early online date	8 Jul 2004
DOIs	https://doi.org/10.1021/ic0496525
Publication status	Published - 1 Aug 2004
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic0496525

Cite this

@article{24ec23294edf438bacfaa1b935fc5093,

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

abstract = "Reaction of sodium hydrotris(methimazolyl)borate (NaTmMe) with cobalt halides leads to the formation of paramagnetic pseudotetrahedral [Co(TmMe)X] (X = CI, Br, I), of which the bromide has been crystallographically characterized. Mass spectrometry reveals the presence of higher molecular weight fragments [Co(TmMe)2]+ and [Co2(TmMe)2X]+ in solution. Aerial oxidation in donor solvents (e.g. MeCN) leads to formation of the [Co(TmMe)2]+ cation, which has been crystallographically characterized as the BF4-, C1O 4-, Br-, and I-, salts. Attempts to prepare the mixed sandwich complex, [Co(Cp)(TmMe)]+, resulted in ligand decomposition to yield [Co(mtH)3I]I (mtH = 1-methylimidazole-2-thione), but with the more electron donating methylcyclopentadienyl (CpMe) ligand, [Co(CpMe)(Tm Me)]l was isolated and characterized. Electrochemical measurements reveal that the cobalt(III) TmMe complexes are consistently more difficult to reduce than their Tp and Cp congeners.",

author = "Dodds, {Christopher A.} and Lehmann, {Mario Alexander} and Ojo, {Jonathan F.} and John Reglinski and Spicer, {Mark D.}",

year = "2004",

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doi = "10.1021/ic0496525",

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volume = "43",

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journal = "Inorganic Chemistry",

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TY - JOUR

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

AU - Dodds, Christopher A.

AU - Lehmann, Mario Alexander

AU - Ojo, Jonathan F.

AU - Reglinski, John

AU - Spicer, Mark D.

PY - 2004/8/1

Y1 - 2004/8/1

N2 - Reaction of sodium hydrotris(methimazolyl)borate (NaTmMe) with cobalt halides leads to the formation of paramagnetic pseudotetrahedral [Co(TmMe)X] (X = CI, Br, I), of which the bromide has been crystallographically characterized. Mass spectrometry reveals the presence of higher molecular weight fragments [Co(TmMe)2]+ and [Co2(TmMe)2X]+ in solution. Aerial oxidation in donor solvents (e.g. MeCN) leads to formation of the [Co(TmMe)2]+ cation, which has been crystallographically characterized as the BF4-, C1O 4-, Br-, and I-, salts. Attempts to prepare the mixed sandwich complex, [Co(Cp)(TmMe)]+, resulted in ligand decomposition to yield [Co(mtH)3I]I (mtH = 1-methylimidazole-2-thione), but with the more electron donating methylcyclopentadienyl (CpMe) ligand, [Co(CpMe)(Tm Me)]l was isolated and characterized. Electrochemical measurements reveal that the cobalt(III) TmMe 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(TmMe)X] (X = CI, Br, I), of which the bromide has been crystallographically characterized. Mass spectrometry reveals the presence of higher molecular weight fragments [Co(TmMe)2]+ and [Co2(TmMe)2X]+ in solution. Aerial oxidation in donor solvents (e.g. MeCN) leads to formation of the [Co(TmMe)2]+ cation, which has been crystallographically characterized as the BF4-, C1O 4-, Br-, and I-, salts. Attempts to prepare the mixed sandwich complex, [Co(Cp)(TmMe)]+, resulted in ligand decomposition to yield [Co(mtH)3I]I (mtH = 1-methylimidazole-2-thione), but with the more electron donating methylcyclopentadienyl (CpMe) ligand, [Co(CpMe)(Tm Me)]l was isolated and characterized. Electrochemical measurements reveal that the cobalt(III) TmMe complexes are consistently more difficult to reduce than their Tp and Cp congeners.

U2 - 10.1021/ic0496525

DO - 10.1021/ic0496525

M3 - Article

AN - SCOPUS:3843092695

SN - 0020-1669

VL - 43

SP - 4927

EP - 4934

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 16

ER -

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

Abstract

ASJC Scopus subject areas

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