Premium
New Alkyl−Cobalt(III) Complexes with Tridentate Amino−Oxime Ligands: Synthesis, Structure, and Reactivity
Author(s) -
Dreos Renata,
Felluga Alessandro,
Nardin Giorgio,
Randaccio Lucio,
Siega Patrizia,
Tauzher Giovanni
Publication year - 2001
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(20011)2001:1<267::aid-ejic267>3.0.co;2-z
Subject(s) - chemistry , steric effects , reactivity (psychology) , alkyl , stereochemistry , corrin , oxime , cobalt , oxidative addition , ligand (biochemistry) , octahedron , lithium diisopropylamide , medicinal chemistry , halide , crystallography , crystal structure , ion , deprotonation , organic chemistry , catalysis , medicine , biochemistry , alternative medicine , receptor , pathology
The oxidative addition of alkyl halides to the Co I species generated by the reduction of [Co III (LNHpy)(HLNHpy)](ClO 4 ) 2 ( 1 ), where HLNHpy is the tridentate 2‐(2‐pyridylethyl)amino‐3‐butanone oxime ligand and LNHpy is its conjugate base, led to the formation of a new class of organocobalt complexes of general formula [RCo III (LNHpy)(HLNHpy)](ClO 4 ) [R = Me ( 2a ), Et ( 2b ), CH 2 CF 3 ( 2c ), n Bu ( 2d ), and CH 2 Cl ( 2e )]. All the complexes were characterised by 1 H and 13 C NMR spectroscopy. The X‐ray structures of 2a , 2b and 2c provide evidence for a pseudo‐octahedral configuration, where HLNHpy and LNHpy act as bi‐ and tridentate ligands, respectively. The axial geometry in 2a is closer to that found in methylcobalamin than that reported for other models, suggesting steric and electronic cis influences of the equatorial ligands close to those of the corrin nucleus. The solution properties and the reactivity show strong analogies with those of the previously known Vitamin B 12 models.