NDLI: Synthesis and characterization of redox-active tris(pyrazolyl)borate cobalt complexes

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Dalton Transactions Vol - 0 Issue - 7

Dalton Transactions Vol - 0 Issue - 6

Dalton Transactions Vol - 0 Issue - 5

Synthesis and characterization of redox-active tris(pyrazolyl)borate cobalt complexes

Content Provider	Royal Society of Chemistry (RSC)
Author	Daengngern, Rathawat Harding, Phimphaka Adams, Harry Yimklan, Saranphong Harding, David J.
Copyright Year	2009
Abstract	The reaction of CoX2 (X = Cl, Br, NO3) with KTpPh2 in tetrahydrofuran (THF) yields the half-sandwich compounds [TpPh2CoX] (X = Cl 1, Br 2, NO33). The reaction of [TpPh2CoBr] with NaX (X = N3, NO2) or potassium thiocyanate (KNCS) permits isolation of [TpPh2CoX] (X = N34, NCS 5, NO26). In contrast, the reaction of cobalt(II) acetate with KTpPh2 yields [TpPh2Co(OAc)(HpzPh2)] 7 as a result of B–N bond cleavage. Subsequent reaction of 7 with a range of β-diketones in the presence of NaOMe produces the β-diketonate complexes, [TpPh2Co(β-diketonate)] (β-diketonate = acac 8, hfac 9, dbm 10, tmhd 11). IR spectroscopy suggests that the TpPh2 ligands are κ3-coordinated and that the β-diketonate ligands adopt a bidentate coordination mode. Electronic spectra are consistent with four- or five-coordinate species in solution. X-Ray crystallographic studies of 7 reveal an intermediate five-coordinate cobalt centre with a hydrogen bonding interaction between the pyrazole hydrogen and the acetate carbonyl oxygen. The molecular structures of 9 and 10 show cobalt centres with square pyramidal coordination geometries and κ2-coordinated β-diketonate ligands. Cyclic voltammetric studies of 6 reveal irreversible one-electron reduction to Co(I). However, the β-diketonate complexes, 8, 10 and 11 undergo irreversible one-electron oxidation. The redox potential and reversibility increases as the steric bulk of the substituent on the β-diketonate ligand increases.
Starting Page	1314
Ending Page	1320
Page Count	7
File Format	HTM / HTML PDF
ISSN	14779226
Volume Number	0
Issue Number	8
Journal	Dalton Transactions
DOI	10.1039/b815001j
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	NCS Tetrahydrofuran Potassium thiocyanate List of N34 roads Cobalt(II) acetate Chemical bond Dbm Infrared spectroscopy Denticity Cobalt Hydrogen bond Pyrazole Carbonyl group Nucleophile Redox Substituent Ligand
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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