В металло-карбеноидах чем больше катион щелочного металла, тем стабильнее молекула

Рис 1. Иллюстрация к обсуждаемой статье, выведенная на обложку журнала Agewandte Chemie International Edition и приуроченная к Чемпионату Европы по футболу. Футболист с надписью Na/K (натрий и калий) выбивает из молекулы карбеноида мяч с надписью Li — литий. Смена лития на натрий или калий делает необычную молекулы карбеноида стабильной, вопреки интуиции.

Металло-карбеноиды — необычные и очень нестабильные молекулы, которые тем не менее важны для многих реакций в органическом синтезе. До недавнего времени не было известно ни одной такой молекулы, стабильной при комнатной температуре и с расшифрованной молекулярной структурой. В новой работе группы из Вюрцбурга (Германия) исследователям удалось выделить и охарактеризовать сразу три карбеноида с разными щелочными металлами. Оказалось, что, вопреки установившейся металлоорганической парадигме, карбеноиды с более тяжелыми щелочными металлами натрием и калием более стабильны, чем с литием. Авторы предложили объяснение необычному феномену и продемонстрировали его использование в синтезе карбеновых комплексов палладия.

Известная всем поваренная соль NaCl — это ионное соединение между щелочным металлом (натрием) и галогеном (хлором). Ионные связи — одни из наиболее крепких в химии, и самые крепкие ионные связи — именно между щелочными металлами (литий Li, натрий Na, калий K и т. д.) и галогенами (фтор F, хлор Cl, бром Br и т. д.). Чем тяжелее металл и легче галоген — тем связь сильнее (например, из приведенных выше самая прочная пара — это KF, фторид калия). В таких ионных парах щелочной металл отдает один электрон галогену, получается щелочной металл с зарядом плюс (катион) и галоген с зарядом минус (анион).

Ионная связь очень крепкая, и если спланировать химическую реакцию так, чтобы среди ее продуктов получалась соль, то эта реакция скорее всего будет энергетически выгодна и пройдет на ура. В органической химии одна из основных задач — получение связи углерод–углерод (C–C), ведь углерод — основа жизни, ключевой элемент в биомолекулах. На заре органической химии исследователи готовили одни соединения углеводородов с галогенами, другие — с щелочными металлами и потом пытались слить одни с другими в надежде, что выделится соль и получится связь С–С.

Получить cоединения углеводородов с галогенами оказалось относительно несложно. Пожалуй, самое известное широкой публике — хлороформ СНСl3 — было получено аж в начале XIX века. Соединения углеводородов с щелочными металлами (карбанионы) научились делать только через 100 лет после хлороформа — в начале XX века. Тогда же было сформулировано правило: чем больше (тяжелее) щелочной металл (Li 

В металло-карбеноидах чем больше катион щелочного металла, тем стабильнее молекула

Рис. 3. Известные изолированные карбеноиды (1, 3, 4), и их кремневый аналог — силиленоид (2). Ph — фенил, Et2O — диэтиловый эфир, THF — тетрагидрофуран (ТГФ) — циклический эфир, пунктиром обозначается сольватирующая связь с ионом. Сольватирующую связь могут создавать как молекулы растворителя, так и атомы внутри молекулы карбеноида (например, атомы серы в карбеноиде 3). Рисунки из обсуждаемой статьи в Agewandte Chemie International Edition и из статьи G. Molev et al., 2006. Synthesis, molecular structure, and reactivity of the isolable silylenoid with a tricoordinate silicon

В силиленоиде на атоме кремния одновременно сидят атомы фтора и лития. К большому сюрпризу исследователей, рентгеноструктура силиленоида показала, что литий с кремния перескочил на фтор, будто соль LiF вот-вот готова элиминировать. И, наконец, в 2007 году группа Лe-Флош из Палезо впервые опубликовала сведения о карбеноиде, стабильном при комнатной температуре (T. Cantat et al., 2007. From a stable dianion to a stable carbenoid). Стабилизация была достигнута путем использования специальных заместителей с фосфором и серой. Этот карбеноид — разделенная ионная пара, литий отошел от углерода и связан сольватирующей связью с атомами серы и двумя молекулами эфира (молекула 3 на рис. 3).

Однако с одной молекулой много каши не сваришь. Чтобы понять природу стабильных карбеноидов, разобраться, что полезного с ними можно сделать, нужны были новые — подобные, но иные — молекулы. И вот теперь группа Гесснер из Вюрцбурга опубликовала работу, в которой были синтезированы сразу три новых карбеноида: с литием, натрием и калием на атоме углерода с хлором. Один из заместителей углерода сернофосфорный, как у Ле-Флош, а второй — кремневый, (почти) как у Апелоига (молекула 4 на рис. 3).

Сразу после синтеза исследователям стало понятно, что они столкнулись с чем-то неожиданным. Литиевый карбеноид (4–Li) оказался нестабильным выше 0°C, в то время как натриевый (4–Na) и калиевый (4–K) аналоги оставались стабильными до 30°C. 4–Li выделить и кристаллизовать не удалось, но кристаллические структуры 4–Na и 4–K были расшифрованы (рис. 4, А и В). Получается, что карбеноиды ведут себя обратным образом, нежели карбанионы: чем больше катион и полярнее связь с углеродом, тем стабильнее молекула! Чтобы найти дополнительное подтверждение такому наблюдению, авторы решили проверить его на литиевом карбеноиде, добавив к нему краун-эфир. Kраун-эфир полностью сольватирует катион, создавая разделенную ионную пару и тем самым поляризуя связь. Догадка подтвердилась: более поляризованный литиевый карбеноид с краун-эфиром сохранял стабильность до 20°C, что позволило его кристаллизовать и расшифровать молекулярную структуру (рис. 4, С).

В металло-карбеноидах чем больше катион щелочного металла, тем стабильнее молекула

Рис. 4. Молекулярные структуры карбеноидов, расшифрованные рентгенокристаллографией. А — натриевый карбеноид 4–Na. Мономерная структура. Атом натрия отошел от углерода и находится в контакте с хлором, серой и тремя молекулами тетрагидрофурана (ТГФ). B — калиевый карбеноид 4–K. Димерная структура. Калий контактирует с хлором, серой, молекулой ТГФ и фенильным кольцом кремневого заместителя (но не с карбеноидным углеродом). C — литиевый карбеноид, сольватированный краун-эфиром 4–Li(12–crown–4)2. Мономер — разделенная ионная пара. Рисунок из обсуждаемой статьи в Agewandte Chemie International Edition

Проанализировав полученные структуры и использовав квантомеханические расчеты, авторы предложили возможное объяснение наблюдаемому феномену. Как упоминалось выше, при поляризации связи металл–углерод углерод получает избыток отрицательного заряда. В обычном карбанионе избыток отрицательного заряда сбросить некуда, и молекула становится более реактивной (менее стабильной). Однако в карбеноиде это приводит к тому, что избыток заряда переходит на галоген. Полярность связи галоген–углерод снижается, и молекуле в целом так «комфортнее», то есть стабильность молекулы растет, и элиминация соли затрудняется.

Также авторы предложили, как можно использовать их открытие. Чем молекула стабильнее, тем она селективнее реагирует (производит меньше побочных продуктов). Чтобы проверить стабильные карбеноиды в действии, молекулы 4–Li, 4–Li(12–crown–4)2, 4–Na и 4–K были прореагированы с тетрафосфиновым комплексом палладия Pd(PPh3)4 для получения карбенового комплекса 5 (рис. 5).

Карбеновые комплексы переходных металлов — очень важные молекулы, среди которых многие используются в индустрии в качестве катализаторов. Так, например, за открытие метатезиса олефинов, катализируемого карбеновыми комплексами некоторых переходных металлов (молибдена, вольфрама и рутения), в 2005 году Роберту Граббсу и Ричарду Шроку вручили Нобелевскую премию. Карбеновые комплексы редко получаются напрямую реакцией нестабильного карбена с металлом, часто приходится прибегать к синтетическим ухищрениям. Поэтому реакция на рис. 5 представляет особый интерес.

В металло-карбеноидах чем больше катион щелочного металла, тем стабильнее молекула

Рис. 5. Реакция карбеноидов (4–М, где М = Li, Na, K) с тетрафосфиновым комплексом палладия Pd(PPh3)4 с получением карбенового комплекса 5. Формально, в результате реакции с карбеноида элиминирует соль, получившийся карбен привязывается к палладию вместо трех молекул фосфина PPh3. Атом серы тоже привязывается к палладию. Термин «формально» употреблен здесь потому, что досконально механизм реакции не исследовался и, возможно, она идет в другом порядке или с дополнительными промежуточными стадиями. Рисунок из обсуждаемой статьи в Agewandte Chemie International Edition

Анализ продуктов показал, что в реакции с 4–Li получается лишь 47% комплекса 5 (остальные 53% — побочные продукты). Из 4–Li(12–crown–4)2 получается 93% желаемого продукта, а из 4–Na и 4–K выход продукта 5 составил более 99%. Это дополнительное подтверждение стабилизации карбеноидов более тяжелыми щелочными металлами.

С публикацией этой работы стало понятно, почему так тяжело было стабилизировать карбеноиды. Просто химики руководствовались логикой, которая верна для карбанионов: пытаясь выделить литиевые карбеноиды, не обращали внимание на калиевые и натриевые аналоги, которые, оказывается, более стабильны.

Источник: elementy.ru

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