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.

Structural determination of ruthenium-porphyrin complexes relevant to catalytic epoxidation of olefins

E. Gallo;A. Caselli;F. Ragaini;S. Fantauzzi;A. Sironi;S. Cenini
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.
X-ray crystal; highly efficient oxidation; pyridine n-oxides; trans-dioxoruthenium(VI) porphyrins; dioxoruthenium(VI) porphyrins; enantioselective epoxidation; asymmetric epoxidation; aerobic epoxidation; molecular-structure; alkene epoxidation
Settore CHIM/03 - Chimica Generale e Inorganica
INORGANIC CHEMISTRY
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/16401
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