Водородно-связанные интермедиаты и механизмы реакций с переносом протона в химии гидридов переходных металлов тема диссертации и автореферата по ВАК РФ 02.00.08, доктор химических наук Белкова, Наталия Викторовна

• Белкова, Наталия Викторовна
• доктор химических наук
• 2011

Заключение диссертации по теме «Химия элементоорганических соединений», Белкова, Наталия Викторовна

выводы

1. Развито новое научное направление исследования механизма реакций с переносом протона с участием гидридных комплексов переходных металлов, позволяющее выявлять структуру водородно-связанных интермедиатов, термодинамические и кинетические параметры отдельных стадий реакций и факторы воздействия на процесс и реакционную способность гидридов переходных металлов. Разработанный подход включает комбинированное экспериментальное (методами молекулярной спектроскопии (ИК, УФ, ЯМР) в широком диапазоне температур) и квантово-химическое исследование особенностей строения интермедиатов и поверхности потенциальной энергии.

2. Впервые представлен двуямный энергетический профиль реакции переноса протона, протекающей с образованием комплекса с молекулярным водородом через диводородную связь (МЫ-•■НА). Показано, что он имеет общий характер для протонирования гидридов переходных металлов, а образование диводородной связи вносит существенный вклад в энергетику процесса.

3. Установлено, что неклассические продукты протонирования стабилизированы за счёт образования Н-связи между диводородным лигандом и гомосопряженным анионом кислоты, [M(r|2-H2)]+—[ROHOR]. Показано, что термодинамические параметры образования молекулярного и ионного водородно-связанных комплексов возрастают симбатно.

4. Для близких к линейным диводородных связей установлена корреляция между расстоянием г(Н--Н) и рассчитанной энтальпией образования этих комплексов. На основании экспериментальных данных и результатов квантово-химических расчётов показано, что структура ДВС комплексов электронобогатых переходных металлов может отклоняться от линейной из-за присутствия дополнительного взаимодействия с атомом металла. Вклад последнего растёт вниз по группе и для гидридов металлов третьего переходного ряда создаёт возможность прямого переноса протона к атому металла.

5. Показано, что перенос протона происходит внутрикомплексно и в реакции принимает участие вторая молекула протонодонора: МН—НА + НА - МН-НА--НА ^—~ [М(л-Н2)]т[АНА] . Кинетика процесса подчиняется общему уравнению, однако наблюдаемый характер зависимости констант скорости от концентрации НА определяется величинами констант равновесия образования диводородно-связанных интермедиатов.

6. Установлено, что свободная энергия активации переноса протона (AG*pt) линейно уменьшается с ростом прочности диводородной связи (AH°dhb)- Большое отрицательное значение энтропии активации переноса протона (ЛБ^т) свидетельствует об упорядоченном переходном состоянии и определяет уменьшение Ав^рт при понижении температуры.

7. Установлен механизм изомеризации кинетических продуктов переноса протона [М(т12-Н2)]+ в термодинамические [М(Н)г]+. Показано, что образование транс-[Ср*М(Н)2(с1рре)]+ (М = Ре, 11и, Об) требует диссоциации водородно-связанных ионных пар и происходит внутримолекулярно через высокоэнергетическое тригонально-бипирамидальное Переходное СОСТОЯНИе. АН^ош не зависит от природы металла, тогда как величины энтропии активации (АБ^ош) увеличиваются вниз по группе, определяя уменьшение барьера (ДО*,3от) от Ре к Об. Низкобарьерная трансформация [М(г|2-Н2)]+ в [М(Н)2]+ является обратимой и не требует значительного изменения геометрии катиона и диссоциации ионных пар, например, для [Ср*Мо(г12-Н2)(Ъ)(Р2)]+ (Ь = СО, (Н)г; Рг = арре, (РМез)г).

8. Разработан подход к экспериментальному разделению неспецифического (изменение полярности) и специфического (протоноакцепторная/протонодонорная способность) влияния среды. Экспериментально и теоретически установлено, что протонодонорные растворители усиливают диводородно-связанные комплексы за счёт кооперативного эффекта, понижают барьер переноса протона и смещают равновесие в сторону ионных форм. Возможность останавливать реакцию за счет изменения природы растворителя на стадии комплекса с молекулярным водородом либо классического дигидрида показана на примере протонирования Ср*МоН(СО)(РМе3)2 сильной кислотой НВр4-Е1:20 в ТГФ или СН2С12, соответственно, и определяется различиями в специфической сольватации ионных пар.

9. Принципиальная возможность направлять реакцию в сторону образования классического полигидрида или продукта выделения водорода, варьируя температуру, полярность и координирующую способности среды, показана на примере протонирования Ср*Мо(с1рре)Н3 трифторуксусной кислотой. Определены активационные параметры выделения Н2, которые свидетельствуют о диссоциативном характере этой стадии.

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