Супрамолекулярные металлокомплексные каталитические системы для нефтехимического синтеза
Диссертация
В середине 70-х годов компанией КиЬгсЬеггпе-Шюпе-Рои1епс был получен патент на проведение гидроформилирования пропена в водной среде с применением в качестве катализатора комплекса родия с сульфированным трифе-нилфосфином. После реакции водная фаза легко отделялась от продуктов реакции и могла быть использована повторно. С тех пор создание водорастворимых металлокомплексных катализаторов… Читать ещё >
Содержание
- Глава 1. Иммобилизованные на растворимых молекулах комплексы металлов в катализе (Обзор литературы)
- 1. 1. Макромолекулярные металлокомплексные катализаторы, используемые в неполярных растворителях
- 1. 2. Катализ с использованием растворимых терминально функционапизированных полиэфиров
- 1. 3. Макромолекулярные комплексы на основе полиамидов и поликислот. 33 1.41 Катализ растворимыми дендримерами
- 1. 5. Комплексы металлов с лигандами на основе других полимеров
- 1. 6. Макромолекулярные катализаторы на основе макроциклических рецепторов
- 1. 6. 1. Использование макроциклических рецепторов в качестве компонентов ф) каталитических систем
- 1. 6. 1. 1. Реакции окисления
- 1. 6. 1. 2. Реакции с участием водорода и монооксида углерода
- 1. 6. 1. 31. Прочие реакции
- 1. 6. 2. Катализ металлокомплексами с лигандами на основе молекулрецепторов.841.6.2.1. Реакции окисления, катализируемые комплексами металлов! с молекулами-рецепторами
- 1. 6. 2. 2. Гидрирование и гидроформилирование
- 1. 6. 1. Использование макроциклических рецепторов в качестве компонентов ф) каталитических систем
- 211. Окисление циклогексана пероксидом водорода в присутствии комплексов терминально-функционализированных полиэфиров и ионов железа
- 2. 2. Окисление этилбензола пероксидом водорода в присутствии полиэфирных макрокомплексов железа (Ш)
- 2. 3. Окисление углеводородов кислородом воздуха в присутствии макрокомплексов кобальта
- 2. 4. Окисление непредельных соединений в присутствии макромолекулярных катализаторов на основе полиэфиров
- 2. 4. 1. Окисление олефинов кислородом до метилкетонов в присутствии макрокомплексов палладия
- 2. 4. 2. Эпоксидирование непредельных соединений в условиях Макаямы
- 2. 5. Гидроксилирование ароматических соединений пероксидом водорода в присутствии макрокомплексов железа
- 3. 1. Гидрирование диоксида углерода в муравьиную кислоту на макрокомплексах рутения и родия в мягких условиях
- 4. 1. Каталитические системы на основе циклодекстринов и каликсаренов в Вакер-окислении непредельных соединений
- 4. 1. 1. Вакер-окисление алкенов с использованием молекул-рецепторов в качестве компонентов каталитических систем
- 4. 1. 2. Окисление алкенов-1 с использованием комплексов палладия с молекулами-рецепторами
- 4. 1. 3. Вакер-окисление циклогексенов и стиролов
- 4. 1. 4. Использование подхода молекулярного импринтинга для создания каталитических систем на основе молекул-рецепторов
- 4. 2. Окисление ароматических соединений с использованием каталитических систем на основе циклодекстринов
- 4. 2. 1. Гидроксилирование ароматических соединений пероксидом водорода
- 4. 2. 2. Окисление алкилароматических соединений пероксидом водорода
- 5. 1. Исходные вещества
- 5. 2. Анализ исходных веществ, катализаторов и продуктов реакции
- 5. 2. 1. Анализ методом высокоэффективной жидкостной хроматографии
- 5. 2. 2. Анализ методом газо-жидкостной хроматографии
- 5. 2. 3. Анализ методом масс-спектрометрии
- 5. 2. 4. Анализ методами атомно-адсорбционной и атомно-флуоресцентной спектроскопии
- 5. 2. 5. Анализ методом ЯМР спектроскопии
- 5. 2. 6. Анализ методом ИК-спектроскопии
- 5. 2. 7. Анализ методом УФ-спектроскопии
- 5. 2. 8. Анализ методом рентгено-фотоэлектронной спектроскопии (РФЭС)
- 5. 2. 9. Определение устойчивости комплексов «гость-хозяин» с макроциклическими рецепторами
- 5. 2. 10. Моделирование строения комплексов «гость-хозяин» между каликсаренами и алкенами методом молекулярной механики
- 5. 3. Синтез катализаторов, использованных в работе
- 5. 3. 1. Синтез полимерных макролигандов
- 5. 3. 2. Получение макрокомплексов переходных металлов с полиэтиленоксидом, терминально функционализированным ацетилацетоном .,
- 5. 3. 3. Синтез нанесенных макромолекулярных комплексов родия и рутения. 308 5.3.4 Синтез лигандов на основе модифицированных ß--циклодекстринов
- 5. 3. 5. Синтез металлокомплексов на основе циклодекстринсодержащих лигандов
- 5. 3. 6. Синтез модифицированных циклодекстринов с использованием темплатов
- 5. 3. 7. Синтез каликсаренов и каликсаренсодержащих лигандов
- 5. 4. Методика проведения каталитических экспериментов
- 5. 4. 1. Каталитическое окисление олефинов
- 5. 4. 2. Гидроксилирование ароматических соединений
- 5. 4. 3. Окисление углеводородов пероксидом водорода
- 5. 4. 4. Окисление этилбензола кислородом
- 5. 4. 5. Эпоксидирование алкенов в присутствии изомасляного альдегида
- 5. 4. 6. Гидрирование диоксида углерода в водной среде
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