A reproducible synthesis of a competent epoxidation catalyst, [Ru-VI(TPP)(0)(2)] (TPP = tetraphenylporphyrin dianion), starting from [Ru-II(TPP)(CO)L] (L = none or CH3OH), is described. The molecular structure of the complex was determined by using ab initio X-ray powder diffraction (XRPD) methods, and its solution behavior was in detail investigated by NMR techniques such as PGSE (pulsed field gradient spin-echo) measurements. [Ru-IV(TPP)(OH)](2)O, a reported byproduct in the synthesis of [Ru-VI(TPP)(O)(2)], was synthesized in a pure form by oxidation of [Ru-II(TPP)(CO)L] or by a coproportionation reaction of [Ru-VI(TPP)(O)(2)] and [Ru-II(TPP)(CO)L], and its molecular structure was then determined by XRPD analysis. [Ru-VI(TPP)(O)(2)] can be reduced by dimethyl sulfoxide or by carbon monoxide to yield [Ru-II(TPP)(S-DMSO)(2)] or [Ru-II(TPP)(CO)(H2O)], respectively. These two species were characterized by conventional single-crystal X-ray diffraction analysis.
Structural determination of ruthenium-porphyrin complexes relevant to catalytic epoxidation of olefins / E. Gallo, A. Caselli, F. Ragaini, S. Fantauzzi, N. Masclocchi, A. Sironi, S. Cenini. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 44:6(2005), pp. 2039-2049. [10.1021/ic048587w]
Structural determination of ruthenium-porphyrin complexes relevant to catalytic epoxidation of olefins
E. GalloPrimo
;A. CaselliSecondo
;F. Ragaini;S. Fantauzzi;A. SironiPenultimo
;S. CeniniUltimo
2005
Abstract
A reproducible synthesis of a competent epoxidation catalyst, [Ru-VI(TPP)(0)(2)] (TPP = tetraphenylporphyrin dianion), starting from [Ru-II(TPP)(CO)L] (L = none or CH3OH), is described. The molecular structure of the complex was determined by using ab initio X-ray powder diffraction (XRPD) methods, and its solution behavior was in detail investigated by NMR techniques such as PGSE (pulsed field gradient spin-echo) measurements. [Ru-IV(TPP)(OH)](2)O, a reported byproduct in the synthesis of [Ru-VI(TPP)(O)(2)], was synthesized in a pure form by oxidation of [Ru-II(TPP)(CO)L] or by a coproportionation reaction of [Ru-VI(TPP)(O)(2)] and [Ru-II(TPP)(CO)L], and its molecular structure was then determined by XRPD analysis. [Ru-VI(TPP)(O)(2)] can be reduced by dimethyl sulfoxide or by carbon monoxide to yield [Ru-II(TPP)(S-DMSO)(2)] or [Ru-II(TPP)(CO)(H2O)], respectively. These two species were characterized by conventional single-crystal X-ray diffraction analysis.File | Dimensione | Formato | |
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