Галогенофильный механизм и классический механизм присоединения-элиминирования в реакциях нуклеофильного винильного замещения с участием анионов карбонилов переходных металлов тема диссертации и автореферата по ВАК РФ 02.00.08, кандидат химических наук Сазонов, Пётр Кириллович

• Сазонов, Пётр Кириллович
• кандидат химических наук
• 2010

Заключение диссертации по теме «Химия элементоорганических соединений», Сазонов, Пётр Кириллович

ВЫВОДЫ

1. Исследованы реакции карбонилат-анионов ([М(СО)пЦ") с широким кругом винилгалогенидов, отличающихся как природой галогена (На1=Р,С1,Вг,1), так и степенью активации двойной связи и пространственным строением реакционного центра. Изучен состав продуктов и кинетика реакций, показано, что реакции в большинстве случаев происходят с сохранением конфигурации двойной связи.

2. Найден необычный галогенофильный механизм нуклеофильного винильного замещения, первой стадией которого является нуклеофильная атака карбонилат-аниона по атому галогена. Образование продуктов замещения, обычных сг-винильных комплексов УтМ(СО)„Ь или гало(ацил)металлатов [Ут(СО)М(СО)4На1]" М=Ые, Мп, происходит в результате сочетания интермедиатов, винильного карбаниона и М(СО)пЬНа1. Строение гало(ацил)рената впервые охарактеризовано методом РСА.

3. Показано, что нуклеофильная атака карбонилата по атому галогена является общим явлением и выступает в качестве основной альтернативы классическому АёкЕ механизму нуклеофильного винильного замещения. Вероятность галогенофильной реакции увеличивается в ряду С1«Вг«1, большинство винилхлоридов и первичные винилбромиды реагируют по Ас1кЕ механизму. Решающую роль играет строение винилгалогенида: стабильность карбанионных интермедиатов Ас1иЕ или галогенофильной реакций и наличие пространственных препятствий для атаки нуклеофила по двойной связи. Галогенофильный механизм возможен даже в реакциях винилхлоридов с карбонилатами, также как механизм А<1мЕ возможен для винилиодидов.

4. Для сравнения изучены реакции тиолатов и карбанионов с теми же субстратами и показано, что они происходят по обычному АёкЕ механизму, что подтверждает более высокую "галогенофильность" металл-центрированных карбонилат-анионов по сравнению с С- и Б-нуклеофилами.

5. На примере реакций карбонилат-анионов впервые создана субстрат-независимая шкала нуклеофильности для реакций винильного замещения по Ас^Е механизму. Нуклеофильность карбонилатов хорошо коррелирует с их нуклеофильностью в алифатическом замещении, но изменяется в намного более широком диапазоне:

CpFe(CO)2]"»[Re(CO)5]"»[Mn(CO)5]">[CpW(CO)3]">[CpMo(CO)3]" *[M(C0)"L]M' ~1014 7-107 130 5 1

CpMo(CO)j]K

Расширенная шкала нуклеофильности карбонилатов справедлива и для галогенофильных реакций карбонилатов с винилгалогенидами.

6. Найдена корреляция lg(&on<) галогенофильных реакций с линейной комбинацией AEi реакции VinHal —> [Vin]" + Hal+ и АЕг реакции VinHal + [Мп(СО)5]~ —*■ [Vin]- + Mn(CO)sHal, рассчитанных методом DFT.

7. Разработана модель, позволяющая предсказать скорость АёкЕ и галогенофильных реакций винилгалогенидов с карбонилатами, основанная на корреляции экспериментально полученных данных lg(Â'0TII) с рядом параметров, рассчитанных методом DFT. Модель корректно предсказывает направление реакций винилгалогенидов с карбонилатами и позволяет построить ряд электрофильности винилгалогенидов в AcInE и галогенофильных реакциях.

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