Catalytic Silylation of Dinitrogen with a Dicobalt Complex

Randall B. Siedschlag, Varinia Bernales, Konstantinos D. Vogiatzis, Nora Planas, Laura J. Clouston, Eckhard Bill, Laura Gagliardi, Connie C. Lu

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144 Scopus citations


A dicobalt complex catalyzes N2 silylation with Me3SiCl and KC8 under 1 atm N2 at ambient temperature. Tris(trimethylsilyl)amine is formed with an initial turnover rate of 1 N(TMS)3/min, ultimately reaching a turnover number of ∼200. The dicobalt species features a metal-metal interaction, which we postulate is important to its function. Although N2 functionalization occurs at a single cobalt site, the second cobalt center modifies the electronics at the active site. Density functional calculations reveal that the Co-Co interaction evolves during the catalytic cycle: weakening upon N2 binding, breaking with silylation of the metal-bound N2 and reforming with expulsion of [N2(SiMe3)3]-.

Original languageEnglish (US)
Pages (from-to)4638-4641
Number of pages4
JournalJournal of the American Chemical Society
Issue number14
StatePublished - Apr 15 2015

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© 2015 American Chemical Society.


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