83006-01-3Relevant academic research and scientific papers
(Phthalocyaninato)iron(II)- and -ruthenium(II) Compounds with Isocyanides as Axial Ligands
Keppeler, Uwe,Kobel, Wolfram,Siehl, Hans-Ullrich,Hanack, Michael
, p. 2095 - 2104 (2007/10/02)
(Phthalocyaninato)iron(II) and -ruthenium(II) (PcM, M = Fe, Ru) react with aliphatic and aromatic monodentate isocyanides RNC (R = t-Bu, c-HX, Bzl, Ph, Me2ph) with formation of the corresponding bisaxial substituted (phthalocyaninato)metal(II) compounds PcM(RNC)2 (M = Fe, Ru) 1-5.The structures of these soluble compounds were determined by 1H and 13C NMR spectroscopy.The influence of the central metal atom M and of the organic group on the ?-donor-?-acceptor properties of the metal-ligand bonds is investigated by IR spectroscopy.UV/VIS spectroscopy , TG/DTG/DTA measurements and FD mass spectroscopy additionally demonstrate the large differences when changing iron against ruthenium in 1-5.The thermal and mass spectroscopic differences point to the existence of pentacoordinated PcRu(II) compounds.
Comparative kinetics of axial ligation to ruthenium and iron porphyrin and phthalocyanine complexes. Relationship between spin state and cis and trans effects
Pomposo, Frank,Carruthers, David,Stynes, Dennis V.
, p. 4245 - 4248 (2008/10/08)
Kinetic data for the dissociative axial substitution reactions of benzyl isocyanide (BzNC) and CO complexes of ruthenium octaethylporphyrin (OEP), tetraphenylporphyrin (TPP), and phthalocyanine (Pc) complexes are reported and compared with corresponding data for iron complexes. The relative lability of BzNC complexes containing 1-methylimidazole (CH3Im) and 4-tert-butylpyridine (t-Bupy) is RuPc a spin change occurring along the reaction coordinate for ligand dissociation is proposed to account for an additional ～3 kcal/mol lower ΔG? only in the iron porphyrin systems. Trans effects of CO and BzNC are rationalized in terms of spin-state effects in the transition state.
