94943-91-6Relevant academic research and scientific papers
Metalloporphyrins with metal-metal bonds. Synthesis and characterization of (P)InMn(CO)5, (P)InCo(CO)4, and (P)InM(CO)3Cp where M = Cr, Mo, and W. Molecular stereochemistry of [(2,3,7,8,12,13,17,18-octaethylporphyrinato)indium(III)]pentacarbonylmanganese
Guilard,Mitaine,Mo?se,Lecomte,Boukhris,Swistak,Tabard,Lacombe,Cornillon,Kadish
, p. 2467 - 2476 (2008/10/08)
The synthesis and physicochemical characterization of 10 metal-metal-σ-bonded indium porphyrins were investigated in nonaqueous media. The ligands σ-bonded to indium tetraphenylporphyrin ((TPP)In) or indium octaethylporphyrin ((OEP)In) were Mn(CO)5, Co(CO)4, W(CO)3Cp, Mo(CO)3Cp, and Cr(CO)3Cp. Each neutral complex was characterized by 1H NMR, IR, and UV-visible spectroscopy. On the basis of these data, the presence of a single metal-metal covalent bond was suggested, and this was confirmed by a room-temperature single-crystal X-ray diffraction study. (OEP)InMn(CO)5 crystallizes in the triclinic system, space group P1. Its lattice constants are as follows: a = 12.415 (3) A?, b = 13.485 (2) A?, c = 15.083 (3) A?, α = 61.99 (2)°, β = 69.69 (2)°, and γ = 69.75 (2)° with Z = 2 (Dexptl = 1.44 g·cm-3), R(F) = 0.041, and Rw(F) = 0.048 for 7346 unique reflections. The In-Mn bond length is 2.705 (1) A?, and the indium atom lies 0.744 (1) A? from the plane of the four porphyrin nitrogens. The average Mn-CO equatorial distance (1.839 (4) A?) is longer than the axial one (1.809 (6) A?). The electrochemistry of each σ-bonded complex was carried out in methylene chloride containing 0.1 M (TBA)PF6. Each metalloporphyrin could be electrooxidized, but the bimetallic complex underwent a rapid cleavage of the metal-metal bond after the first one-electron abstraction. The complexes could also be reversibly reduced by one or two electrons, but a cleavage of the metal-metal bond invariably occurred, leading to formation of (P)In? and [ML]- entities. Some of the reduced compounds were stable for short times that depended upon the specific axial ligand. In these cases a characterization of the reduced species was carried out. Finally, comparisons were made between the reactivities and physicochemical properties of the investigated complexes and other alkyl or aryl σ-bonded indium porphyrins that have been described in the literature.
Metal-metal bonds extended over a porphyrin ring. 1. Syntheses of (TPP)Sn-M(CO)n-1-Hg-M(CO)n and (TPP)In-M(CO)n (M(CO)n = Mn(CO)5, Co(CO)4) and X-ray molecular structure analysis of (TPP)Sn-Mn(CO)4-Hg-Mn(CO)5·1/2CH2Cl 2
Onaka, Satoru,Kondo, Yoshinori,Yamashita, Masahiro,Tatematsu, Yukinobu,Kato, Yoshio,Goto, Masafumi,Ito, Tasuku
, p. 1070 - 1076 (2008/10/08)
The title compounds have been synthesized by the reaction of (TPP)SnCl2 with Hg[Mn(CO)5]2 and Hg[Co(CO)4]2 or by the reaction of (TPP)InCl with Mn2(CO)10 and Co2(CO)8. The structure of (TPP)Sn-Mn(CO)4-Hg-Mn(CO)5 has been solved at room temperature. It crystallizes in the trinclinic system, space group P1. Its lattice constants are a = 14.79 (4) ?, b = 14.87 (3) ?, c = 13.49 (2) ?, α = 92.3 (2)°, β = 111.3 (2)°, and γ = 109.3 (3)° with Z = 2. The molecule contains a bent four metal atom unit, (TPP)Sn-Mn(1)(CO)4-Hg-Mn(2)(CO)5, extended over the porphyrin ring with a right angle at Mn(1). The observed Sn-Mn bond length, 2.554 (7) ?, is the shortest one yet observed for tin-manganese bonded compounds, and the tin atom lies about 0.85 ? above the plane defined by the four nitrogen atoms of the porphyrin ring. All the synthesized compounds show very strong absorptions at around 450 nm and strong absorptions in the 340-390-nm region. 1H and 13C NMR have been measured for these compounds.
