RESUMO
A new polyoxovanadium cluster compound, [VO6{(OCH2CH2)2N(CH2CH2OH)}6]·0.5CH3CN, was synthesized and characterized by single-crystal X-ray diffraction analysis, FTIR and UV-vis spectroscopy, and TGA. The cluster is composed of a fully reduced cyclic {V6N6O18} framework, which adopts an Anderson-like structure and is comprised of a ring of six edge-sharing {VO5N} octahedra incorporating six {(OCH2CH2)2N(CH2CH2OH)} ligands. Two (OCH2CH2-) arms of each of the six triethanolamine ligands are directly incorporated into the oxometalate core and the third {-CH2CH2OH} arm remains pendant. In the condensed phase, the clusters form discrete hcp layers through inter-cluster hydrogen bonding. These layers stack through soft chemical interactions to form a 3D network structure. The neutral cluster, [VO6{(OCH2CH2)2N(CH2CH2OH)}6], is the isopolyoxovanadium analogue to the cationic clusters contained in a series of heteropolyoxovanadium compounds previously introduced by our laboratory, e.g., [LiVO6{(OCH2CH2)2N(CH2CH2OH)}6]+; its existence shows that a heteroatom is not required to form or stabilize the common organofunctionalized vanadium oxide framework: [VO6{(OCH2CH2)2N(CH2CH2OH)}6]. To the best of our knowledge, the isopolyoxovanadium and heteropolyoxovanadium clusters represent the first reported isopoly-heteropoly analogues in the polyoxometalate field. We compare the TGA profile, FTIR and UV-vis spectra of the new compound with two of its cationic heteropoly analogues.
RESUMO
A new heteropolyoxovanadium compound, [NaV6O6{(OCH2CH2)2NH}6]·(OH)0.5Cl0.5·3(H2O), was synthesized and characterized by single-crystal X-ray diffraction analysis, cyclic voltammetry, FTIR and UV-vis spectroscopy, and TGA. [NaV6O6{(OCH2CH2)2NH}6]·(OH)0.5Cl0.5·3(H2O) contains the diethanolamine functionalized oxovanadium cationic cluster, [NaV(IV)6O6{(OCH2CH2)2NH}6](+). The cluster cation is composed of a fully reduced cyclic {NaV6N6O18} framework which adopts an Anderson-like structure and is comprised of a ring of six edge-sharing {VO5N} octahedra linked to a central {NaO6} unit. Two (OCH2CH2-) arms of each of the six diethanolamine ligands are incorporated into the oxometalate core. FTIR spectra are consistent with the presence of expected V=Ot stretching modes and functionalization with diethanolamine. Electrochemical and UV-vis absorption properties are consistent with two distinct MLCT processes: the characteristic V=Ot dπ-pπ interaction, and a second process occurring through the hydrogen-terminated nitrogen atoms (V-N-H) of the octahedra forming the cyclic {NaV6N6O18} core.
RESUMO
(C5Me5)3Sm reacts with the free radical 2,2,6,6-tetramethylpiperidinyl-1-oxy (TMPO) to form (C5Me5)2 and the per nitroxide [(eta 1-ONC5H6Me4)2Sm(mu-eta 1:eta 2-ONC5H6Me4)]2.
RESUMO
The hydrothermal reaction of V2O5, V2O3, 2,2'-bpy and Na2SO4 in dilute sulfuric acid yields a novel hybrid, [VIVO(mu 3-SO4)(2,2'-bpy)]infinity, which demonstrates the potential of constructing a new class of robust composite solids composed of a (V/O/SO4)-based framework decorated with organic functionalities by combining appropriate vanadyl sulfate motifs with a variety of organic ligands.
RESUMO
The system IrX(CO)[P(C(6)H(5))(3)](2) in benzene solution adds mo lecular oxygen reversibly if X is chlorine and irreversibly if X is iodine. The crystal structure of the complex IrIO(2)(CO)[P(C(6)H(5))(3)](2) * CH(2)Cl(2) is reported here and compared with a previous study of the structure of IrClO(2)(CO)[P(C(6)H(5))(3)](2). The O-O bond length is 1.47 +/- 0.02 angstroms in the irreversibly oxygenated iodo-compound and 1.30 +/- 0.03 angstroms in the reversibly oxygenated chloro compound.
