110589-22-5Relevant academic research and scientific papers
Synthesis of Bis(aliphatic amine)osmium(II), Bis(arylamido)osmium(IV), and Bis(imido)and Oxo(imido)osmium(VI) Porphyrins
Li, Zao-Ying,Huang, Jie-Sheng,Chan, Michael Chi-Wang,Cheung, Kung-Kai,Che, Chi-Ming
, p. 3064 - 3071 (2008/10/09)
The syntheses, characterization, and reactivity of a series of osmium porphyrins, OsII(Por)(H2NR)2 [Por = dianions of octaethylporphyrinato (OEP), tetraphenylporphyrinato (TPP), meso-tetrakis(p-tolyl)porphyrinato (TTP), mesotetrakis(4-chlorophenyl)porphyrinato (4-Cl-TPP), meso-tetrakis(3,4,5-trimethoxyphenyl)porphyrinato (3,4,5-MeO-TPP). R = tBu; Por = TPP, R = iPr], OsII(Por)(HNEt2)2 (Por = TPP, 3,4,5-MeO-TPP), OsIV(Por)(NHAr)2 (Por = OEP, TPP, 3,4,5-MeO-TPP; Ar = Ph, 4-F-Ph). OsVI(Por)(NtBu)2 (Por = TPP, TTP, 4-C1-TPP, 3,4,5-MeO-TPP), OsVIO(Por)(NtBu) (Por = TPP, TTP, 4-C1-TPP, 3,4,5-MeO-TPP), and OsVIO(Por)(4-F-PhN) (Por = TPP, 3,4,5-MeO-TPP) are described. The complexes Os(Por)(HNAr)2 are prepared from the reactions of Os(Por)-(N2)(THF) with arylamines in aerobic tetrahydrofuran. Air oxidations of Os(Por)(H2NtBu)2 in tetrahydrofuran and in the presence of H2NtBu give OsO(Por)(NtBu) and Os(Por)(NtBu)2. The X-ray crystal structures of OsO-(TTP)(NtBu)·EtOH and Os(4-Cl-TPP)(NtBu)2 have been determined. Crystal data for OsO(TTP)(NtBu)·EtOH: monoclinic, space group P2l/c, a = 13.546(6) A, b = 23.180(3) A, c - 16.817(3) A, β = 90.84(2)°, V = 5279.7-(1.0) A3, Z = 4. Os(4-Cl-TPP)(NtBu)2: monoclinic, space group P2l/c, a = 11.046(2) A. b = 18.380(3) A, c = 23.640(4) A, β= 97.22(1)°, V = 4759.8(1.0) A, Z = 4. The Os=O and Os=NtBu distances in OsO(TTP)-(NtBu)·EtOH are 1.772(7) and 1.759(9) A, respectively. The Os=NtBu distances in Os(4-Cl-TPP)(NtBu)2 average 1.775 A. The imido angles range from 165.8(8) to 170.6(9)°. For the infrared spectra of these complexes, a discussion on the "oxidation state marker" band in the vicinity of 1000 cm-1 is presented. The differences in the electronic properties of osmium porphyrins at various oxidation states are also described.
Synthesis and Spectroscopy of tert-Butylimido Complexes of Osmium(VI) and Ruthenium(VI) Porphyrins
Huang, Jie-Sheng,Che, Chi-Ming,Poon, Chung-Kwong
, p. 161 - 163 (2007/10/02)
Oxidative deprotonation of gives , and , which are characterised by IR and 1H NMR spectroscopy.
Synthesis, reactivity, and X-ray structural characterization of trans-dioxoosmium(VI) porphyrin complexes
Che, Chi-Ming,Chung, Wai-Cheung,Lai, Ting-Fong
, p. 2801 - 2804 (2008/10/08)
The oxidation of [Os(P)(CO)(EtOH)] (P = porphyrin dianion) to [Os(P)(O)2] by m-chloroperoxybenzoic acid in CH2Cl2 proceeds through a stable Os(IV) intermediate. The [Os(p-X-TPP)(O)2] (X = Cl, H, OMe, Me) and [Os
Redox Reactions of Osmium Porphyrins
Mosseri, Shlomo,Neta, Pedatsur,Hambright, Peter,Sabry, Dina Y.,Harriman, Anthony
, p. 2705 - 2712 (2007/10/02)
The metal centre in osmium porphyrinates (OsP) can exist in a wide range of oxidation states, each being stabilised by axial complexation with a particular ligand.Thus OsIIP is stabilised by ligation with a CO molecule.Oxidation occurs readily to form the corresponding OsIIIP which retains the CO ligand and can be reduced quantitatively to the originalOsII complex.Further oxidation gives OsIVP which is stabilised by axial ligation of two alcohol or water molecules.These OsIV complexes are stable to both oxidation and reduction.Treating the OsIIP with an organic peroxide results in formation of an OsVIP complex which is stabilised by two oxo ligands but can be reduced to the OsIVP species.Photolysis of OsIIP and OsIIIP causes loss of the CO ligand, the naked porphyrin species so formed undergoes oxidative reactions with the solvent, O2, or trace impurities, in most cases forming an OsIVP complex.The VIP(O)2> species does not oxidise alkanes or alkenes in the dark at room temperature but does oxidise cyclohexene under visible light irradiation.
