Formation and reactivity of paramagnetic organometallic nickel complexes of 21-oxa- and 21-selenaporphyrins—1H NMR and EPR investigations
作者： Ewa Pacholska , Piotr J. Chmielewski , Lechosław Latos-Grażyński
DOI: 10.1016/S0020-1693(97)06006-4
关键词: Inorganic chemistry 、 Metal 、 Reactivity (chemistry) 、 Chemistry 、 Electron paramagnetic resonance 、 Aryl 、 Nickel 、 Ligand 、 Bond cleavage 、 Proton NMR 、 Crystallography
摘要: Abstract Addition of aryl Grignard reagents to a toluene solution nickel(II) monohalide complexes 5.20-bis( p -tolyl)-10.15-diphenyl-21-oxaporphyrin (ODTDPPH) and 5.20-diphenyl-10.15-bis( -tolyl)-21-selenaporphyrin (SeDPDTPH) at 203 K resulted in formation paramagnetic σ -aryl derivatives which were identified characterized by means 1 H NMR. The coordination the ligand has been unambiguously proven unique downfield pattern corresponding resonances. ( -aryl)nickel(II) are high-spin electronic state: (d xv ) 2 vz z x y . A homolytic cleavage Ni 11 -C bond determined for (ODTDPP)Ni II (Ar) (SeDPDTP)Ni with low-valent nickel species: (SeDPDTP)Ni. One-electron reduction Cl generate investigated EPR, involving 61 isotope enrichment spectral simulations. considerable increase metal d-orbital contribution singly occupied molecular orbital observed upon 1-methylimidazole
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