{"id":85581,"date":"2000-03-07T00:00:00","date_gmt":"2000-03-07T00:00:00","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/polipirazolilborato-complejos-de-cobre-i-como-catalizadores-en-reacciones-de-transformacion-de-olefinas-en-ciclopropanos-aziridinas-y-epoxidos\/"},"modified":"2000-03-07T00:00:00","modified_gmt":"2000-03-07T00:00:00","slug":"polipirazolilborato-complejos-de-cobre-i-como-catalizadores-en-reacciones-de-transformacion-de-olefinas-en-ciclopropanos-aziridinas-y-epoxidos","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/quimica\/polipirazolilborato-complejos-de-cobre-i-como-catalizadores-en-reacciones-de-transformacion-de-olefinas-en-ciclopropanos-aziridinas-y-epoxidos\/","title":{"rendered":"Polipirazolilborato complejos de cobre (i) como catalizadores en reacciones de transformaci\u00f3n de olefinas en ciclopropanos, aziridinas y ep\u00f3xidos"},"content":{"rendered":"<h2>Tesis doctoral de <strong> M\u00aa Del Mar D\u00edaz Requejo <\/strong><\/h2>\n<p>Los complejos bpcu, bpcul (l=bipy, dppe, pcy3) y bpcu(l)2 (l=pph3, piridina) catalizan la reacci\u00f3n de ciclopropanaci\u00f3n de olefinas, utilizando diazoacetato de etilo como fuente de carbeno. Experimentos de competici\u00f3n con estirenos parasustituidos han permitido sugerir la existencia de un intermedio catal\u00edtico com\u00fan en la reacci\u00f3n de descomposici\u00f3n del eda por dichos complejos: el complejo bpcu.  estudios cin\u00e9ticos han permitido proponer un esquema mecan\u00edstico para la reacci\u00f3n de descomposici\u00f3n del eda en ausencia y en presencia de olefina, partiendo asimismo del complejo bpcu o de cualquiera de sus aductos. La especie catal\u00edticamente activa es el fragmento de 14 electornes bpcu, que se genera la partir de los aducto complejos una esepcie metal-carbeno, de corta vida, que puede reaccionar con una segunda mol\u00e9cula de eda o, alternativamente, con una mol\u00e9cula de olefina para producir, respectivamente, fumarato y maleato de dietilo o el correspondiente cilcopropano. La presencia de oelfina y\/o ligandos l en el medio de reacci\u00f3n supone una dismincui\u00f3n de kla especie catal\u00edticamente activa, bpcu, debido a la formaci\u00f3n de complejos del tipo bpcul y\/o bpcu(olefina) y en consecuencia un en lentecimiento de lproceso catal\u00edtico.  los complejos bpcu, tp*cu(c2h4), tp*cu y bpz4cu pueden absorberse sobre gel de s\u00edlice mediante el proceso de impregnaci\u00f3n en este sopotte de disoluciones de estos complejos. Se han determinado las cantiades absorbidas de cobre por gramo de gel de s\u00edlice, observ\u00e1ndose que el grado de adsorcion aumenta en el orden bpcu &lt; tp*cu &lt;bpz4cu.  la interacci\u00f3n complejo soporte se puede explicar mediante la formaci\u00f3n de enlaces dehidr\u00f3geno cl\u00e1sicos y no cl\u00e1sicos entre los grupos hidroxilos de la superficie del soporte y los enlaces b-h o los \u00e1tomos de nitr\u00f3geno de los anillos de pirazol no coordinados al centro met\u00e1lico.<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>Polipirazolilborato complejos de cobre (i) como catalizadores en reacciones de transformaci\u00f3n de olefinas en ciclopropanos, aziridinas y ep\u00f3xidos<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 Polipirazolilborato complejos de cobre (i) como catalizadores en reacciones de transformaci\u00f3n de olefinas en ciclopropanos, aziridinas y ep\u00f3xidos <\/li>\n<li><strong>Autor:<\/strong>\u00a0 M\u00aa Del Mar D\u00edaz Requejo <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Huelva<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 03\/07\/2000<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n<h3>Direcci\u00f3n y tribunal<\/h3>\n<ul>\n<li><strong>Director de la tesis<\/strong>\n<ul>\n<li> P\u00e9rez Romero Pedro Jos\u00e9<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: ernesto Carmona guzm\u00e1n <\/li>\n<li>roberto S\u00e1nchez delgado (vocal)<\/li>\n<li>maurice Brookhart (vocal)<\/li>\n<li> Vilchez mart\u00edn Jos\u00e9 Carlos (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de M\u00aa Del Mar D\u00edaz Requejo Los complejos bpcu, bpcul (l=bipy, dppe, pcy3) y bpcu(l)2 (l=pph3, piridina) catalizan [&hellip;]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"site-sidebar-layout":"default","site-content-layout":"","ast-site-content-layout":"","site-content-style":"default","site-sidebar-style":"default","ast-global-header-display":"","ast-banner-title-visibility":"","ast-main-header-display":"","ast-hfb-above-header-display":"","ast-hfb-below-header-display":"","ast-hfb-mobile-header-display":"","site-post-title":"","ast-breadcrumbs-content":"","ast-featured-img":"","footer-sml-layout":"","theme-transparent-header-meta":"","adv-header-id-meta":"","stick-header-meta":"","header-above-stick-meta":"","header-main-stick-meta":"","header-below-stick-meta":"","astra-migrate-meta-layouts":"default","ast-page-background-enabled":"default","ast-page-background-meta":{"desktop":{"background-color":"var(--ast-global-color-4)","background-image":"","background-repeat":"repeat","background-position":"center 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